Nadal, No. 2 in the world, takes on world No. 26 Juan Monaco in the first match of the best-of-five series Friday. Ferrer, ranked fifth, is paired against 11th-ranked Juan Marin del Porto.
The 2011 Davis Cup final is being played on a red clay court at the Olympic Stadium in Seville, Spain.
The Argentina-Spain pairing is a rematch of the 2008 finals, which was won by Spain 3-1. Spain has won the Davis Cup title four times. In addition to the 2008 title, Spain titled in 2000, 2004 and 2009.
Argentina is looking for its first championship. It has been the runner-up three times -- 1981, 2006 and 2008. Argentina is 0-3 versus Spain, having lost in the 2008 finals, 2003 semis and 1926 quarters.
Nadal is 2-1 in his career versus Monaco but they haven't played since 2007. Ferrer and del Porto have split their four previous meetings.
After Friday's singles matches, the schedule calls for doubles Saturday when Argentines David Nalbandian and Eduardo Schwank are to team against Spain's Feliciano Lopez and Fernando Verdasco.
Nadal faces del Potro in the first singles match Sunday with Ferrer and Monaco scheduled for the final of the series.