Former world number one Marat Safin will open Russia's Davis Cup title defence on Friday, while untested Igor Kunitsyn will play in the doubles after injury ruled out team mate Dmitry Tursunov.
Thursday's draw pitted Safin against Chile's Nicolas Massu in the opening rubber of their World Group first round tie in the Chilean resort of La Serena.
The match appears the most evenly balanced of the ties, and Chilean coach Hans Gildemeister said it could well determine the outcome of the three-day contest.
"Russia are obliged to win that point," he told a news conference. "Safin is a former world number one. If they lose that point it'll make things very complicated for them.
"Nicolas has got a good chance of winning that match."
In the second singles rubber, Chile's Australian Open finalist and world number five Fernando Gonzalez squares off against Igor Andreev, ranked 147.
Tursunov, a key member of the team which won last year's title, had been expected to play in Saturday's doubles but withdrew with a wrist injury just before the draw.
The inexperienced Kunitsyn will take his place alongside Georgian-born Teimuraz Gabashvili, against the far more experienced pairing of Massu and Gonzalez.
Russia were already fielding a weakened team after world number three Nikolay Davydenko and world number 22 Mikhail Youzhny opted not to make the long trip to Chile.
The defending champions are up against a Chilean team which has not lost at home in their last nine Davis Cup outings.
