Corretja, 39, has been in charge for the past two years after replacing Albert Costa, who led the Spanish to the Davis Cup title in 2009 and again in 2011.
Under Corretja, they reached last year's final where they lost 3-2 to the Czech Republic.
"On the advice of the Sports Department and a unanimous decision by the management committee, it has been decided not to re-appoint Alex Corretja as captain of the men's national team on December 31," the Federation announced in a written statement.
"Federation President Jose Luis Escanuela Romana thanks Alex Corretja for his dedication and his professionnalism and wishes him all the best."
No mention was made of a possible successor.
As a player, Corretja achieved a career high ranking of 2 in 1999. He was twice runner up in the French Open — in 1998 and 2001