In Addition to the Isley Brothers sample, the song features use of keyboards, synthesizers and electric guitars. The song is a slow jam love song and the lyrics describe the persona's desire to be rich in love, simultaneously comparing her lover with luxuries. The song also features Stefani's husband Gavin Rossdale who opens the song in French. The song was released as the album's fifth single in late 2005 (see 2005 in music) along with a remix. A music video featuring rapper Slim Thug was also released which featured the Harajuku Girls as well. The track received mixed reviews from critics, who generally found the track less impressive than the previous singles. It entered the top forty worldwide but had mediocre success overall and was less popular than the previous singles from L.A.M.B.
After Stefani and Kanal finished writing "Luxurious", they visited record producer Nellee Hooper, who suggested a sample of The Isley Brothers' "Between the Sheets". The song had previously been sampled in several songs such as Da Brat's "Funkdafied", Jim Jones' "Summer Wit Miami", The Notorious B.I.G.'s "Big Poppa", and Whitney Houston's "One of Those Days". Stefani was reluctant to use the sample because it would mean losing some of the publishing rights to the song. Nevertheless, she decided to use it because "it sounded so amazing and meant to be".
"Luxurious" is a slow jam love song with instrumentation from keyboards and synthesizers. It is written in common time in the key of A minor. The song uses a descending i-vii-VI-V chord progression. The lyrics of the song include descriptions of wealth and riches, what one reviewer called "a world of Egyptian cotton, cashmere, tuberoses, and, of course, diamonds". Stefani stated that "[the] song really is more about a love relationship. If you really listen to the lyrics, it has nothing to do with money or luxury. It has to do with love, being rich in love. I just wanted to think of a clever way to express how you have to work really hard for the rewards of that." The single version of the song contains an additional verse from rapper Slim Thug for release to urban radio and clubs.
The song begins with Stefani's husband Gavin Rossdale speaking in French. and then leads into the first verse. The lyrics describe Stefani talking about "flying first class" and "livin' like a queen". She talks about being luxuriously in love and calls her lover Limousine and Treasure Chest. She talks about the increasing passion between her and her partner, and says, "Our passion it just multiplies" and "got in the fifth gear, baby". In the chorus she tells that love is getting expensive and she and her partner have to work hard night and day to be rich in love, and after working hard, when they lay back together, they get the payback. After the second verse, the song gets slower and Stefani repeats "Cha-ching, cha-ching" four times alternated with lines talking about getting "hooked up with the love" and "hydroponic love". The song ends with Gavin Rossdale speaking more lines in French.
"Luxurious" had mediocre success in North America. In the United States, the single debuted on the Billboard Hot 100 on November 5, 2005 at number eighty. It failed to reach the top twenty, peaking at number twenty-one five weeks later, and remained on the chart for twenty weeks. It performed better on the pop-oriented charts, reaching number ten on the Top 40 Mainstream, number thirteen on the Pop 100, and number thirty-seven on the Adult Top 40. The track also had some crossover success, charting at number nine on the Rhythmic Top 40 and number thirty-three on the Hot R&B/Hip-Hop Singles & Tracks. In Canada, the single was released to radio on October 25, 2005. It reached number twenty-one on the Canadian BDS Airplay Chart, and remained in the top one-hundred for twelve weeks. "Luxurious" was more successful on the Canadian Singles Chart, where it peaked at number ten in its sixth week on the chart.
The song was released on December 5, 2005 in Europe and Australia. It received very little promotion in the UK and continued the trend of Stefani's lower-charting singles since "Hollaback Girl" when it debuted at number forty-four and dropped off the UK Singles Chart after only one more week. The single performed similarly throughout Europe, where it reached the top forty in Ireland, Italy, and Switzerland, but generally did not reach the top thirty. Stefani's previous four singles had been successful in Australia, where all reached the top ten; however, "Luxurious" did not reach the top twenty and reached a peak of number twenty-five. In New Zealand, "Luxurious" was moderately successful, where it reached number seventeen but stayed on the chart for only ten weeks.
The music video for "Luxurious" was directed by Sophie Muller. In the video, Stefani plays a chola in high school. Then Stefani, accompanied by her Harajuku Girls, receive a manicure at a beauty salon, and styling her hair and applying cosmetics in front of a mirror. She shows off gold jewellery with her name carved on it. During his rap, Slim Thug appears in sequences with Stefani or two Harajuku Girls. It concludes with Stefani joining her friends in a block party, where they celebrate with breakdancing and a barbecue. The video is intercut with sequences of Stefani breaking open piñatas and lying on a candy-covered floor.
Stefani had generally developed music video concepts while writing the song, but since she had not expected "Luxurious" to become a single, she had not given much thought to a music video for the song. The image she had for her persona was a high school girl named Mercedes, who she described as "very inspiring":
Stefani called Muller, who had directed several videos for Stefani and No Doubt, to direct the music video. Muller did not understand Stefani's vision for the video, so Stefani became involved in developing ideas for the video.
The video had mediocre success on music video programs. On MTV's Total Request Live, the video debuted on October 25, 2005 at number ten. It peaked at number seven and left the countdown after only five days. After its October 21 debut on MuchMusic's Countdown, it peaked at number eleven nine weeks later, remaining on the chart for thirteen weeks. The video was featured on an episode of MuchMusic's Video on Trial, where the reviewers found it a superficial attempt to market to various races.
Some vinyl copies accidentally have the Slim Thug remix twice on side A.