Anastasia Pavlyuchenkova will face Jelena Jankovic in the opening singles match Saturday when Russia hosts Serbia in the Fed Cup semifinals.
Two-time Grand Slam champion Svetlana Kuznetsova will face former French Open champion Ana Ivanovic in the second match.
Serbia has reached the semifinals of the tournament for the first time and, with the two former No. 1-ranked players on the team, is considered the favorite.
Russia, a four-time champion, has beaten Serbia in all three of their previous meetings, but is without its two top players: Maria Sharapova and Vera Zvonareva.
''It's going to be a historic moment for us.'' Jankovic said. ''Hopefully we could make it into the final. It's been a long way to come up to this stage (of the competition). It will be a tough match. We are playing against Russia and in Russia.''
Ivanovic, whose was in doubt because of the flu, said she was ready for the match.
''I think, we have really good chances (to win),'' she said. ''We had good preparation and good team spirit and it's the biggest chance for us and we all want to make most of it.''
The last time the two teams played, in Belgrade in the first round in 2010, Russia won 3-2.
Jankovic won both of her singles matches, while Ivanovic lost twice, and the two players then were beaten by the Russian duo of Kuznetsova and Alisa Kleybanova in the decisive doubles match.
''This time it will be a tough match, for sure,'' Serbia captain Dejan Vranes said. ''But we have worked hard and our team is ready for the match. We'll try our best to win.''
Sharapova was not scheduled to play in the best-of-five series, while Zvonareva was dropped from the team because of a shoulder injury.
''In this situation, it was clear that Kuznetsova will play singles,'' Russia captain Shamil Tarpischev said. ''But we had several options for the second player in the singles and the decision to name Pavlyuchenkova as No. 1 was taken in the last minute.''
Another option was Maria Kirilenko, who is 1-3 in two appearances for Russia but has the highest WTA ranking among the four players at No. 21.
Pavlyuchenkova is 3-0 against Jankovic on the WTA Tour, while the 27th-ranked Kuznetsova is 2-6 against Ivanovic.
Ivanovic downplayed the statistics.
''It's always tough to play them (Russians) on the WTA Tour,'' Ivanovic said. ''And the Fed Cup is different from the tour tournaments because there is much more at stake. You are playing for your country and it's always very, very open.''
In Sunday's reverse singles, Pavlyuchenkova will take on Ivanovic, while Kuznetsova will play Jankovic. In doubles, the Russian pair of Kirilenko and Elena Vesnina will face the Serbian duo of Bojana Janovski and Aleksandra Krunic.
The reverse singles and doubles nominations can be changed depending on the results of the previous matches.
The winner will play either the Czech Republic or Italy in the final on Nov. 3-4.
