Ferrer was not expected to make himself available for the July 17-19 match in Vladivostok following a dispute between top players and the Spanish tennis federation (RFET) over the appointment last year of Gala Leon as the nation's first female Davis Cup captain.
After weeks of upheaval at the federation and the naming of a new president, Leon was sacked last week and Martinez, a former Wimbledon champion who is also Spain's Fed Cup captain, was named to replace her until the end of the year.
Ferrer, who pulled out of Wimbledon on the eve of the tournament with an elbow injury, will be joined in the Spain team by Pablo Andujar, Daniel Gimeno-Traver, Marc Lopez and David Marrero, Martinez told a news conference in Barcelona.
The five-times winners, missing the likes of Rafa Nadal, Feliciano Lopez and Tommy Robredo, need a victory to have a chance of getting back into the elite World Group for next year's competition.
"I did not have much time to put the team together," Martinez said.
"It has been a difficult situation because two days before the squad announcement everyone had their commitments and calendar plans, all important, and it wasn't easy.
"I have the support of almost all (the players) for the next match but this one was more difficult.
"When I spoke to David he first said he wasn't going to make it but he then said he had spoken to the doctor and would do physio and in the end he said he could play after all.
"We have a great team to get through the tie and put ourselves in a position to secure promotion."
Leon replaced Carlos Moya after the former world number one stood down when Spain were relegated from the World Group following defeat by Brazil.
Nadal, Ferrer and others questioned her appointment, with some of their main criticisms being that she was under-qualified and did not know the players.
Naming Martinez appears to have addressed some of those concerns, at least for Ferrer, who is currently Spain's highest ranked player ahead of Nadal at number 10.
Russia named their team on Tuesday featuring the relatively little-known Konstantin Kravchuk, Evgeny Donskoy, Andrey Rublev and Karen Khachanov.
(This story has been refiled to fix spelling of Khachanov in final paragraph)
(Writing by Iain Rogers, editing by Ken Ferris)
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