The second-ranked Nadal helped Spain beat France 4-1 in the semifinals to set up the Dec. 2-4 final on indoor clay at the Olympic Stadium in Seville.
Fifth-ranked David Ferrer will play singles alongside Nadal, while Feliciano Lopez and Fernando Verdasco are expected to play doubles.
Spain captain Albert Costa also included Marcel Granollers and Marc Lopez as playing partners. Granollers is coming off a victory at the Valencia Open.
The four-time champions begin training in Seville on Saturday, with Nadal and Ferrer joining them after the ATP World Tour Finals.
Spain beat Argentina in the 2008 final.