The five-time winners, now captained by Conchita Martinez, were hoping to win a place in the World Group Playoff next September and return to the game's elite but instead they went down in the best-of-five matches in Vladivostok.
Spain missed star names such as Rafa Nadal and David Ferrer but they were still clear favourites in the three-day Group 1 tie against a Russian team without a player in the ATP top 100.
They started well with Tommy Robredo and Pablo Andujar winning their first two games but then Evgeny Donskoy and Konstantin Kravchuk beat Marc Lopez and David Marrero in the doubles to trigger a slide.
Robredo lost to Donskoy and youngster Andrey Rublev was too strong for Andujar in the final contest.
Spain were competing in Group 1 for the first time since 1996 following their shock defeat by Brazil last September and this further loss puts their future in the second tie in jeopardy.
It has been a turbulent time for Spanish tennis with the appointment of Martinez earlier this month, replacing the unpopular Gala Leon, giving her little time to prepare for the match.
Leon was the surprise choice by the federation, due to her lack of experience, to become Spain's first female Davis Cup captain following the Brazil defeat and she lacked the backing of many of the top players.
There had already been a poor relationship between the federation and the players who felt that they did not receive enough backing.
On top of this, federation president Jose Luis Escanuela stood down earlier this month after a financial probe by the government led to his suspension.
(Editing by Amlan Chakraborty)
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