Kirilenko, whose Fed Cup experience was limited to two matches five years ago, was tagged as Russia's No. 2 by captain Shamil Tarpischev in Friday's draw.
Vera Zvonareva, who was expected to lead the home side on an indoor hard-court at Olympic Stadium, was forced to pull out because of the shoulder injury that has been troubling her for the last two weeks.
"Zvonareva's absence is a big loss for us," Tarpischev said. "We would have been much stronger with her. But it was clear that in her current form and without her serve, she would have been the weakest one on the team."
Kvitova said it will not be easy to beat Russia even without Zvonareva.
"I think they are still strong. It (the final) is still wide open, 50-50," she said.
Kvitova has had a remarkable season. The Czech started the year ranked outside the top 30 but won Wimbledon for her first Grand Slam title and beat Victoria Azarenka in the WTA Championships final in Istanbul on Sunday to claim her sixth title this year and improve to No. 2 in the rankings.
She has a 9-4 record in the Fed Cup, winning all four singles in two ties this season. She says she was not tired after the long season.
"I will play 100 percent for sure and, actually. I'm not tired," the 21-year-old Kvitova said.
Kirilenko beat Kvitova the two times they played on the WTA tour in 2009, but both have moved up in the rankings considerably.
"A Fed Cup match differs from the one in a tournament and she will have no advantage that she had won (before)," Kvitova said.
Kirilenko said she expected Anastasia Pavlyuchenkova to be nominated to play in the opening singles, but will be motivated on Saturday.
"When you know that it's the last tournament in the season you always want to play your best," Kirilenko said.
In another surprise move, Tarpischev named doubles specialist Elena Vesnina to substitute for Zvonareva in the doubles.
"The choice was purely tactical," Tarpischev said. "A tie is played in two days, and the second day is always really complicated."
Kuznetsova has an impressive 21-7 Fed Cup record. She's 2-1 against Safarova, who has won only five of her 13 matches in the Fed Cup.
In Sunday's reverse singles, Kvitova is set to play Kuznetsova, then Kirilenko takes on Safarova. In the doubles, Vesnina will partner Pavlyuchenkova against the Czech duo of Lucie Hradecka and Kveta Peschke.
Russia has won the Fed Cup title four times since 2003. The Czechs are five-time winners, but their last final appearance was in 1988 when, as Czechoslovakia, they beat the Soviet Union 2-1.