Carlos Marchena began his career at Sevilla, before moving to Benfica in 2000. Justa  year later, he returned to Spain to join Valencia, the club where he would make the most appearances. During his 9 years at the club, Marchena won 2 La Liga titles, a UEFA Cup and a UEFA Super Cup.

He made 69 appearances for his country, playing in the Olympic Games in 2000, as well as at Euro 2004. At Euro 2008, having won the tournament, he was selected in the Team of the Tournament, and was also part of the squad that won the World Cup in 2010.