A tough-tackling centre back with a reputation as a master of the dark arts of football, Marchena began his career at Sevilla and after a brief stint with Portuguese side Benfica joined Valencia in 2001.
The 36-year-old won two La Liga titles, a UEFA Cup and a King's Cup before moving to Villarreal in 2010 and Deportivo La Coruna two years later. His final club was Indian Super League (ISL) side Kerala Blasters.
Part of a golden generation of Spanish players, Marchena mainly played as a substitute for La Roja, with whom he also won the Under-20 World Cup in 1999 playing alongside the likes of Xavi and Iker Casillas.
"I am putting an end to my active career as a footballer," Marchena, whose 69th and final appearance for Spain came in 2011, said in a letter to fans posted on the national team's website (www.sefutbol.com) on Tuesday.
"It (the decision) was not at all easy but that's life and now it's time to confront a new era," he added.
"I take away from football an education, good friends and a magnificent experience."
(Reporting by Iain Rogers, editing by Ed Osmond)
