She is the eldest of four children of veteran Greek politician Constantine Mitsotakis, who was prime minister of Greece from 1990 to 1993 and leader of the country's conservative party, New Democracy, from 1984 to 1993. Bakoyannis studied political science and public law at the University of Athens, and politics and communication in Munich, Germany. She is fluent in English, French and German.
In 1968, the Mitsotakis family fled to Paris to escape the military dictatorship that ruled Greece for seven years starting in 1967. They returned to Athens in 1974 when military rule collapsed. That same year she married Pavlos Bakoyiannis, a respected journalist and politician. They had two children, Alexia and Kostas. Over the next several years she worked in the Ministry of Economic Co-ordination and, later, the Ministry of Foreign Affairs. In 1984, when her father was elected leader of the New Democracy party, she became his chief of staff.
When her father was elected Prime Minister the following year, Bakoyiannis served first as an Undersecretary of State, and then as Culture Minister. She was elected three times as Member of Parliament for Evritania, and later for Athens, by a sweeping majority. When New Democracy lost the 1993 elections and her father resigned, she successfully ran for a seat in the party central committee. In 2000 the new leader of the party, Kostas Karamanlis, appointed her shadow foreign and defence minister. She is now married to businessman Isidoros Kouvelos. According to Greek family law she is entitled to use any of three surnames, her maiden one, those of her late and current husbands, or any combination thereof: she has chosen to be known by that of her late husband.
In June 2002 the investigation against the November 17 terrorist group intensified, and a series of arrests netted 19 individuals, most of whom have acknowledged being members of the terrorist group. Among them are three men who allegedly confessed to participating in the murder of Pavlos Bakoyiannis.
In the summer of 2002, when Karamanlis was looking for a way to demonstrate his party's growing strength against the ruling Panhellenic Socialist Movement in local elections, he picked Bakoyianni to run for Mayor of Athens. She led a large field of candidates in the first round of the elections in October 2002 and then trounced her Socialist opponent in the run-off a week later with the biggest majority in the city's history.
She successfully hosted what many are calling the best-run Olympics in modern history. She is the first woman to serve as mayor of a city hosting the Olympic Games, the first woman elected to lead Europe's oldest city, Athens, and the most popular politician in her country according to opinion polls. In 2005, in a world wide held poll, she was voted World Mayor.
On February 14, 2006, Dora Bakoyannis was appointed Foreign Minister, under Prime Minister Costas Karamanlis. She is the first ever woman to hold the job. A day after the broad cabinet reshuffle handed her Greece's second highest job, Bakoyannis, who is seen as conciliatory towards neighbouring Turkey, made clear Greece wanted to warm up ties that have been in limbo for several months.
After the defeat of New Democracy in the 2009 elections, Bakoyannis sought to replace Costas Karamanlis as party leader. She lost, after a hard-fought battle, to another former Foreign Minister: Antonis Samaras.