The world number two, currently competing at the U.S. Open in New York, has not represented his country since helping them to a 3-1 triumph against Argentina in the 2011 final in Seville, Spain's fifth victory in the competition.
He will join up with Tommy Robredo, Fernando Verdasco and Marc Lopez for the Sept. 13-15 match on his favoured clay at Madrid's Magic Box arena, Corretja told a news conference.
"Nadal brings vitality and optimism and when I spoke to him in New York he expressed a lot of strength and desire," Corretja said.
"The good news is Rafa is back but the effort made by everyone in the team is the same," he added.
After returning from a knee injury at the start of the year, Nadal has been in scintillating form, claiming a record eighth French Open singles crown as well as Masters titles on the clay at Rome and Madrid and on the hard courts of Indian Wells, Montreal and Cincinnati.
The 27-year-old has won 20 of his 21 Davis Cup singles matches, including 16 on clay, and is unlikely to be given much of a challenge by any of the Ukrainians, whose highest-ranked player is world number 37 Alexandr Dolgopolov.
Second-ranked Spain are in the playoffs after losing away to Milos Raonic's Canada in the first round in February.
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