Her parliamentary career started after the general elections of 2000 when she won a seat for the province of Barcelona and went on to be elected as such in different legislations.
Minister of Housing
Whilst José Luis Rodríguez Zapatero's term, Carme replaced María Antonia Trujillo as Minister of Housing. When already in charge, she had to face the Spanish real estate bubble.
Minister of Defence
April 14, 2008, Chacon was named Minister of Defence. She became the first female Minister of Defence in Spain, which, together with the fact that she was seven months pregnant at the time, was considered a significant development by the press. Interior Minister Alfredo Pérez Rubalcaba temporarily took over the defense portfolio when Chacón gave birth. Shortly after she chose to live in the Ministry's residence, which has its own kindergarten, so as not to waste time travelling between her home and her workplace. That year surveys results points to her as the most influential minister of Mr Zapatero cabinet. In 2009, Carme announced the controversial withdrawal of Spanish troops set in Kosovo due to its unrecognizable independence proclamation for the country. Despite the strong opposition of the US government, the Spanish cabinet agreed with the NATO allies the gradual withdrawal of these troops. In the same year, with the growth of piracy in Somali waters, Carme had to deal with the capture of Alakrana, a Basque trawler. A year after, she justified the delivery of new troops to Afghanistan as she proclaimed there was light at the end of the tunnel. Months later, she travelled to Haiti to decorate dead Spanish soldiers on a helicopter crash and visit those deployed due to an earthquake. , Afghanistan in 2010 At the NATO summit in Lisbon in 2010, she informed that the Spanish Armed Forces would start the transference of two Afghan provinces under their control in 2011, three years before the established date by the Alliance for the retreat of the troops. As a minister, the country's Emergency State of the democracy was decreed for the air traffic controllers' crisis in 2010. She also chaired the meetings of the EU defence ministers while Spain held the European Union's six-month rotating presidency. During this time, she led the negotiations with EADS about €3.5 billion extra funding for the Airbus A400M Atlasmilitary transport. In 2011, the Congreso de los Diputados, the lower house in the Spanish Parliament, adopted a law for the rights and duties of the soldiers. This law allows the soldiers to have an associative activity and creates a committee or Junta de Personal acting as a link between the Ministry and the troops.
38th Federal Congress of PSOE
After Zapatero announced he was not going to run in the 2012 elections, Chacón was expected to run for her party's leadership during autumn 2011. However, after the failure of the PSOE in 2011 local elections, she announced that she was withdrawing from the race. The general election was held early in November 2011, in which Zapatero's government was defeated by the People's Party. She left her post and handed to the new defence minister, Pedro Morenés. In January 2012 she announced her intention to opt for the general secretary of PSOE. According to Chacón, her goal was to "lead a new project" and "raise" the party. However, during the celebration of the 38th Federal Congress of PSOE, Chacón lost against Alfredo Pérez Rubalcaba 487 to 465 votes.
PSOE's Secretary for International Relations
Since PSOE's Extraordinary Congress, celebrated on July 2014, Chacón handled the Socialist party's international relations. When Rubalcaba later announced his resignation after his party's dismal showing in the 2014 European elections, Chacón was widely seen as one of the frontrunners for his replacement, but did not run. She left politics in 2016 to practice law. She was also a member of the European Council on Foreign Relations.