He has a degree in law from the University of Calcutta and has been an advocate and college teacher at some time. He also holds Masters degree in both History and Political Science, and an honorary D. Litt.
He married Suvra Mukherjee on July 13, 1957 and has two sons and a daughter.
He rose through a series of cabinet posts to become the Finance Minister of India from 1982 to 1984. In 1984, he was rated as the best Finance Minister of the World according to a survey of Euromoney magazine. His term was noted for India not withdrawing the last US$ 1.1 billion instalment of an IMF loan. Dr. Manmohan Singh was serving RBI as Governor during Pranab's term as Finance Minister. Sources suggests that Pranab was having hesitation to take over as Finance Minister at 2004 in the cabinet of Dr.Manmohan Singh, who served under him a couple of decades ago. As he did not fully endorse the summary installment of Rajiv Gandhi as the caretaker Prime Minister after Indira Gandhi's assassination, he was not included in Rajiv's cabinet. He left the Congress party for a brief period but re-entered in 1989. His political career revived when P. V. Narasimha Rao chose to appoint him as deputy chairman of the planning commission and subsequently as a union cabinet minister. He served as External Affairs Minister for the first time from 1995 to 1996 in Rao's cabinet. In 1997 he was voted Outstanding Parliamentarian.
He was also president of West Bengal state unit of Congress in 1985.
After Sonia Gandhi reluctantly agreed to join politics, Pranab Mukherjee was one of her key mentors, guiding her through difficult situations with examples of how her mother-in-law, Indira Gandhi would have done things. Mukherjee's unfailing loyalty and competence have led to his closeness to Sonia Gandhi and Manmohan Singh, and helped him gain the prestigious position of Defence Minister of India when the party came to power in 2004.
He has also held the position of Deputy Chairman, Planning Commission from 1991 to 1996.
His talents were on display during the negotiations for the Patent's Amendment Bill in early 2005. The Congress was committed to passing an IP bill, but their allies in the United Progressive Alliance from the Left front had a long tradition of opposing some of the monopoly aspects of intellectual property. Pranab Mukherjee, as Defence Minister, was not formally involved but was roped in for his negotiation skills. He drew on many old alliances including the CPI-M leader Jyoti Basu, and formed new intermediary positions, which included product patent and little else. Then he had to convince his own colleagues including commerce minister Kamal Nath, at one point saying: "An imperfect legislation is better than no legislation. Finally the bill was approved on March 23, 2005.
On 24 October 2006, he was appointed as the External Affairs Minister of India. His replacement in the Defence Ministry is A.K. Antony, a senior Congress Party politician and former Chief Minister of the southern state of Kerala.
Pranab Mukherjee was briefly considered for the post of the largely ceremonial Indian presidency. But his name was subsequently dropped after his contribution in the Union Cabinet was considered practically indispensable. Among Mukherjee's current legacy was the successful signing of the 123 Agreement with the US government and then with the Nuclear Suppliers Group, allowing India to participate in civilian nuclear trade in spite of not having signed the nuclear non proliferation treaty. He was also awarded the Padma Vibhushan, India's second highest civilian honor in 2007.