In the other semi-final Spain, aiming for a first Fed Cup title since 1998, will have their work cut out to avoid a third successive defeat by a formidable France side.
United States captain Zina Garrison would have watched Venus's epic Wimbledon final against fellow American Lindsay Davenport with pride, but also a growing sense of trepidation last Saturday.
Such was the intensity and brutal nature of the three-set contest it was highly unlikely that both players would emerge unscathed to report for duty for the 17-times champions.
Her worst fears were realised on Wednesday when 29-year-old Davenport, who lost 9-7 in the deciding set on Wimbledon's Centre Court, withdrew with the back injury that flared up towards the climax of the cliffhanger.
"I'm very disappointed that Lindsay will not be able to support our team here in Moscow," Garrison said after world number one Davenport's withdrawal tilted the balance firmly towards Russia.
With Serena Williams unavailable after her miserable third-round defeat at Wimbledon, Venus is joined by doubles specialist Corina Morariu, debutant Mashona Washington and Serena's Wimbledon conqueror Jill Craybas, who lost her only previous Fed Cup rubber.
The 25-year-old Venus, who rolled back the years to claim a third Wimbledon title, will have to reproduce that sizzling form if the U.S. are to have any chance against a Russian outfit boasting world number five Elena Dementieva and last year's French Open champion Anastasia Myskina.
KUZNETSOVA OUT
The fact that the tie will be played on an indoor claycourt will also stack the odds in Russia's favour despite them being without four members of the team that beat France in last year's final, including U.S. Open champion Svetlana Kuznetsova.
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Last year's runners-up France have an equally impressive singles line-up with Wimbledon semi-finalist Amelie Mauresmo joined by French Open finalist Mary Pierce for the hardcourt tie in Aix en Provence.
Mauresmo and Pierce starred in France's 2003 final triumph against the U.S. and they should have too much class for a solid but unspectacular Spanish team led by world number 33 Anabel Medina.
Also appearing for Spain is Nuria Llagostera, the world number 39, who won a gold medal in doubles at the Mediterranean Games last week. Medina and Llagostera teamed up to win the crucial doubles rubber in the 3-2 quarter-final defeat of Argentina in April.
Away from the glare of the semi-finals, eight other teams do battle to stay in World Group I next year, with Belgium's clash with Argentina the highlight.
Belgium, the 2001 champions, were thrashed 5-0 by the United States earlier this year, but will welcome back Kim Clijsters for the tie in her home town of Bree.
"I really want to help Belgium to stay in World Group I," said Clijsters, who has not played Fed Cup since April 2004 because of injury. "We can count on massive support in Bree."
In the three other ties Croatia play Germany, the Czech Republic host Italy and Switzerland and Austria clash in Lausanne.