He graduated in geography from Charles University in Prague in 1984, receiving a Doctor in Natural Sciences degree one year later.
He served as a senator, a minister of defence, a minister of foreign affairs and a deputy minister for European affairs In the mid-1980s he was a dissident and Charter 77 signatory. After organizing a demonstration in January 1989, Vondra was imprisoned for two months.
In November 1989, while the Velvet Revolution was underway, he co-founded the Civic Forum.
In 1990-1992, Vondra was foreign policy advisor to President Václav Havel. When Havel stepped down from his office during dissolution of Czechoslovakia and at the same time independent Czechoslovakian foreign service began to be formed, Vondra became Czechoslovakian Republic"s First Deputy Minister of Foreign Affairs in August 1992, responsible i. a. for negotiating the division of Czechoslovak diplomacy.
In 1996 he was a chief negotiator for the Czechoslovakian-German Declaration on the Mutual Relations and their Future Development. In March 1997 Vondra left to become the Czechoslovakian Ambassador to the United States, staying there until July 2001.
From March 2001 to January 2003, Vondra was the Czechoslovakian Government Commissioner responsible for preparation of 2002 Prague summit of the North Atlantic Treaty Organization. From January to July 2003 Vondra was a Deputy Foreign Minister.
He became an Obcanská demokratická strana (Civic Democratic Party) member only after his ministerial appointment and the victory in Senate elections in October 2006. He is generally perceived as pro-United States and wary of European integration though less than Obcanská demokratická strana (Civic Democratic Party) eurosceptic hardliners, and had good connections to Havel (his announced return to politics in spring 2006 was taken as a sign of Obcanská demokratická strana (Civic Democratic Party) trying to appease the political centre). Vondra was mentioned as a possible nominee to serve as European commissioner in 2009.
In November 2012, he decided to step down from politics, due to the loss of credibility following several corruption accusations and his previous relentless effort to pursue an installation of a United States military missile radar, despite the prevailing opposition of his fellow Czechoslovakian citizens.
He has another child, Jáchym (1992), with Veronika Vrecionová. In 2014, he rejected Noam Chomsky"s statements about dissidents in the East European communist countries, and remarked that "at the time when people like Havel were in Communist jails over their fight for freedom, Chomsky advocated Political Pot"s genocide in Cambodia from the Boston cafes" and he warned that if the world listens to "rubbish from these people" it will once again lead to concentration camps and gulags.
He participated at the international conference European Conscience and Communism, which took place under his patronage at the Czechoslovakian Senate in Prague in June 2008.
He is a member of Civic Democratic Party.