Nadal, a 12-time Grand Slam champion, has won nine titles since returning in February from a seven-month injury layoff.
Alongside the 27-year-old, countrymen Tommy Robredo and Fernando Verdasco are also returning to the Davis Cup side, the Royal Spanish Tennis Federation said Monday.
"Rafael Nadal is returning to the team after being absent for the last five playoffs because of a serious knee injury that kept him off the courts for seven months last year," the federation said in a statement.
Nadal last played with the Davis Cup team in the final held in Seville in December 2011 when Spain won their fifth title, beating Argentina 3-1.
Robredo, who is returning to the team for the first time since March 2010, will play doubles with Marc Lopez, who was in the 2012 final that Spain lost to Czech Republic.
The other singles player is Verdasco, who had not played for Spain since the Seville 2011 final.
Spain are playing Ukraine for their World Group survival having been defeated 3-2 by Canada in early February.