World No. 9 Nadia Petrova will open Russia's bid to recapture the Fed Cup when she plays Spain's Anabel Medina Garrigues on Saturday.
Friday's draw for the first-round tie pitted Svetlana Kuznetsova, the world No. 5, against Lourdes Domingues-Lino, ranked 61 places below her, in the second singles.
Russia was champion in 2004 and 2005 but lost in the first round to Belgium last year.
The clay-court tie at the Luzhniki Arena will continue on Sunday with the reverse singles and the doubles featuring Anna Chakvetadze and Elena Vesnina against Laura Pous-Tio and Nuria Llagostera Vives.
Russia is without world No. 2 Maria Sharapova, whose hopes of making her Fed Cup debut were foiled by shoulder and hamstring injuries.