Molik won the bronze medal at the 2004 Summer Olympics in Athens in the women's singles competition beating then world no.3 Anastasia Myskina of Russia in straight sets 6/3 6/4.
Her dad forced Alicia Molik to miss much of the later 2005 season, and in October 2005 announced that she would be taking an extended break in order to recover, including the whole 2006 season. However, her recovery appears to have been faster than expected, and in April 2006 it was announced that Molik would be part of the team for Australia's Fed Cup group matches later that month. However, Australian Davis Cup Captain, David Taylor announced that Molik would not be selected as of lack of match play and rustiness. Instead, rookie Casey Dellacqua took her place.
Molik returned to the main tour much earlier than had first been expected, at the Italian Open in 2006, and won her first match since returning at the French Open of 2006, where she reached the third round. At Wimbledon in 2006, she reached the second round, losing to Katarina Srebotnik of Slovenia
She had high hopes for the 2006 US Open, but was shocked 6–3, 6–2 in the first round by the 17-year old Vania King. She gained revenge over Vania King in the first round of the Guangzhou Open, reaching the quarterfinals after also scoring an upset victory over a top 50 player Lourdes Dominguez Lino. After these wins she broke back into the top 200 at 179 and then played in Tokyo where she defeated Jelena Kostanic 7–5 6–3. Molik then suffered disappointing first round defeats in Bangkok (lost to Vania King 6–1 7–5) and Zürich (lost to Shahar Peer 6–1 6–2).
Molik won a wildcard into the 2007 Australian Open by winning the Australian Open Wildcard Play-offs, where she defeated 16 year old Australian Jessica Moore in the final 6–4 6–4. In preparation for the Australian Open she competed in the 2007 Hopman Cup in Perth and scored victories over world no. 6 Nadia Petrova and Ashley Harkleroad. Molik's final Australian Open warm up tournament was the Moorilla Hobart International were she reached the quarters beating two higher ranked opponents on her way before losing to doubles partner and Indian rising star Sania Mirza. Molik and Mirza reached the quarters of the Hobart tournament before losing a very close match to the number two seeds.
During the Australian Open 2007, Alicia Molik won through her first and second round matches against rising Chinese Taipei doubles talent Yung-Jan Chan and Estonian Kaia Kanepi before losing a 3setter against the eighth seed Patty Schnyder of Switzerland. With her impressive 3rd round performance, Molik improved her then-141 ranking to inside the top 100, the first time since withdrawing from numerous tournaments due to that ear infection. Molik also competed in the 2007 French Open losing 1st Round in singles but winning the Doubles with Mara Santangelo. Molik also played in a Wimbledon warm up tournament in Eastbourne losing to Mel South in the first round 1–6 6–3 7–6 and also lost first round in the doubles to Natalie Dechy and Tiantian Sun 6–2 4–6 6–4. Molik was able to bounce back from these early losses to easily win her first round match at Wimbledon, defeating Russia's Anastasia Rodionova in straight sets, before losing a second round meeting with Serena Williams. Molik is also seeded six in doubles with Mara Santangelo. She and Santangelo made it to the Semi-finals before losing to eventual winners, Cara Black and Liezel Huber. Also competing in the mixed doubles, Molik and partner Jonas Bjorkman made the finals losing to Jelena Jankovic and Jamie Murray.
In 2008 Alicia Molik entered the Perth Hopman Cup where she defeated Lucie Safarova 7–5 6–2 in the first round of the Round Robin competition, before losing to Sania Mirza and Serena Williams in ties involving India and the United States respectively. Her second competition of 2008 was the Medibank International where she again faced Lucie Safarova, Safarova winning 7–6 7–6. Molik won her opening round at the 2008 Australian Open against Estonia's Kaia Kanepi, before falling to 18 year old Czech sensation Nicole Vaidisova, 2–6 3–6.
Molik's singles ranking has continued to drop due to a recent elbow problem. Molik lost in the first round of singles qualifying at the French Open and Wimbledon this year, and has not won a main-draw match since January. Molik has enjoyed erratic success in doubles, where she partnered Tiantian Sun and defeated Cara Black and Liezel Huber who were the number 1 seeds at the tournament in Sydney. She partnered Mara Santangelo at Wimbledon and the French Open, but fell in the first round of competition. Molik received a wildcard into the 2008 Beijing Olympics which she stated as "the best news I've had since 2004." Representing Australia alongside fellow countrywomen Samantha Stosur and Casey Dellacqua, Molik was ousted in the first round by Spanish Maria Jose Martinez Sanchez 6—1, 6—1.
On 5 September 2008, Molik announced her retirement from professional tennis.
| Legend |
| Grand Slam (0) |
| WTA Championships (0) |
| Tier I (1) |
| Tier II (1) |
| Tier III (1) |
| Tier IV & V (2) |
| No. | Date | Tournament | Surface | Opponent in the final | Score |
| 1. | 12 January 2003 | Hobart, Australia | Hard | Amy Frazier | 6–2, 4–6, 6–4 |
| 2. | 8 August 2004 | Stockholm, Sweden | Hard | Tatiana Perebiynis | 6–1, 6–1 |
| 3. | 24 October 2004 | Zurich, Switzerland | Hard (i) | Maria Sharapova | 4–6, 6–2, 6–3 |
| 4. | 31 October 2004 | Luxembourg City, Luxembourg | Hard (i) | Dinara Safina | 6–3, 6–4 |
| 5. | 15 January 2005 | Sydney, Australia | Hard | Samantha Stosur | 6–7(5), 6–4, 7–5 |
| Legend |
| Grand Slam (2) |
| WTA Championships (0) |
| Tier I (1) |
| Tier II (3) |
| Tier III (0) |
| Tier IV & V (1) |
| No. | Date | Tournament | Surface | Partnering | Opponents in the final | Score |
| 1. | 14 June 2004 | Eastbourne, Great Britain | Grass | Magüi Serna | Svetlana Kuznetsova & Elena Likhovtseva | 6–4, 6–4 |
| 2. | 2 August 2004 | Stockholm, Sweden | Hard | Barbara Schett | Emmanuelle Gagliardi & Anna Groenefeld | 6–3, 6–3 |
| 3. | 1 November 2004 | Philadelphia, U.S. | Hard | Lisa Raymond | Liezel Huber & Corina Morariu | 7–5, 6–4 |
| 4. | 17 January 2005 | Australian Open, Melbourne | Hard | Svetlana Kuznetsova | Lindsay Davenport & Corina Morariu | 6–3, 6–4 |
| 5. | 21 February 2005 | Doha, Qatar | Hard | Francesca Schiavone | Cara Black & Liezel Huber | 6–3, 6–4 |
| 6. | 21 March 2005 | Miami Masters, USA | Hard | Svetlana Kuznetsova | Lisa Raymond & Rennae Stubbs | 7–5, 6–7(5), 6–2 |
| 7. | 28 May 2007 | French Open, Paris | Clay | Mara Santangelo | Katarina Srebotnik & Ai Sugiyama | 7–6(5), 6–4 |
To prevent confusion and double counting, information in this table is updated only once a tournament or the player's participation in the tournament has concluded.
| Tournament | 1999 | 2000 | 2001 | 2002 | 2003 | 2004 | 2005 | 2006 | 2007 | 2008 | Career W/L | ||||||||
|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
| Grand Slams | |||||||||||||||||||
| Australian Open | 1R | 3R | 1R | 1R | 1R | 4R | QF | A | 3R | 2R | 12-9 | ||||||||
| French Open | 3R | 1R | 1R | 1R | 1R | 1R | A | 3R | 1R | A | 4–8 | ||||||||
| Wimbledon | 1R | 2R | 2R | 1R | 3R | 3R | A | 2R | 2R | A | 8-8 | ||||||||
| U.S. Open | 1R | 2R | 3R | 2R | 3R | 2R | 1R | 1R | 1R | A | 7-9 | ||||||||
| Grand Slam Win-Loss | 2-4 | 4-4 | 3-4 | 1-4 | 4-4 | 6-4 | 4-2 | 3-3 | 3-4 | 1-1 | 35-34 | ||||||||
| Year-End Championship | |||||||||||||||||||
| WTA Tour Championships | A | A | A | A | A | A | A | A | A | 0-0 | |||||||||
| Olympic Games | |||||||||||||||||||
| Summer Olympics | NH | NH | NH | NH | SF-B | NH | NH | NH | 1R | '''0-0 | |||||||||
| Career Statistics | |||||||||||||||||||
| Year End Ranking | 94 | 115 | 47 | 100 | 35 | 13 | 29 | 163 | 56 | ||||||||||
To prevent confusion and double counting, information in this table is updated only once a tournament or the player's participation in the tournament has concluded.
| Tournament | 1998 | 1999 | 2000 | 2001 | 2002 | 2003 | 2004 | 2005 | 2006 | 2007 | 2008 | Career W/L |
|---|---|---|---|---|---|---|---|---|---|---|---|---|
| Grand Slams | ||||||||||||
| Australian Open | 1R | 1R | 2R | 2R | 3R | A | A | W | A | 1R | 3R | 13-7 |
| French Open | A | 2R | 1R | 1R | 3R | QF | 1R | A | 1R | W | 1R | 14-8 |
| Wimbledon | A | 3R | 3R | 1R | 1R | 2R | 2R | 1R | A | SF | 11-7 | |
| U.S. Open | A | 2R | 1R | 3R | 1R | 1R | 1R | QF | A | 3R | 9-8 | |
| Grand Slam Win-Loss | 0-1 | 4-4 | 3-4 | 3-4 | 4-4 | 5-3 | 1-3 | 11-1 | 0-1 | 14-3 | 2-2 | 47-30 |