Venus, who won an epic final against world number one Lindsay Davenport last week, was paired against 2004 French Open champion Anastasia Myskina in Friday's draw held in Moscow's Olympic Stadium.
Davenport injured her back against Venus, forcing her to pull out of the team, but U.S. captain Zina Garrison was still confident her weakened team can reach the final.
"This whole team has a lot of guts and a lot of strength," Garrison told a news conference.
"Each one of these girls is in tip-top shape and ready to go and that's all I can ask of them."
World number 52 Mashona Washington, who replaced Davenport in the team, will make her Fed Cup debut in the second singles rubber against Elena Dementieva.
"I'm ready to go regardless whether it is a practice or play," she said.
Sunday's action will see two reverse singles followed by a doubles match in which Venus is expected to team up with Corina Morariu against Vera Douchevina and Dinara Safina.
Davenport's withdrawal is a huge blow for the Americans, already missing Venus's younger sister Serena, who is unavailable after her shock defeat in the third round of Wimbledon by Jill Craybas.
The former world number one has been plagued by various injuries this season.
All eyes will now be on Venus, who will have to play a leading role in Moscow if the U.S. are to go through.
"Initially, I was behind Lindsay and Serena and I wasn't expected to be in this position but I feel real good right now," she said.
Garrison added: "Most of all Venus is a leader and everyone including myself will just follow."
"I can trust my team that they can play on any surface," Garrison added of the 17-times Fed Cup champions, who are gunning for their first title since 2000.
"I believe there will be some shocking matches here."
FIRST WIN
Russia captain Shamil Tarpishchev said his team was counting on vocal home support to lift them as they seek their first win against the Americans after losing all four previous ties.
"Definately, we're hoping for a great support both days," he said. "I think fan support counts five or seven percent toward overall victory."
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"The fact that Lindsay is missing gives us an even bigger chance," said Myskina, who celebrated her 24th birthday on Friday.
Dementieva said she would draw inspiration from beating Venus in the 1999 final, the American's only defeat in 13 Fed Cup rubbers.
"I remember it very well. I think they had four players ranked in the top five in the world. It was like playing against a 'Dream Team'," said the Russian.
"But I beat her scoring a consolation point and though we lost 4-1 it gave us a great confidence boost for the future."