Pierce's win gave the French an insurmountable 3-1 lead against Russia -- later reduced to 3-2 by a home victory in the doubles -- knocking the host nation out of the tournament.
Pierce, the former French and Australian Open champion who has not represented her country in Fed Cup since the 1997 final, had too much experience for the 19-year-old Zvonareva, who was playing her third Fed Cup match.
Afterwards, Pierce credited team captain Guy Forget for her victory.
"At the end of the match Guy told me to be more aggressive and just go for my shots," she said. "For some reason I wasn't aggressive enough and he reminded me of that."
What was a joy for France was a huge disappointment for Russia and the thousands of fans in attendance, including former Russian President Boris Yeltsin.
"Of course I'm disappointed, but I think I gained some valuable experience and hopefully next time I won't be that nervous," Zvonareva said.
In the earlier match, world number four Amelie Mauresmo overpowered Anastasia Myskina 6-7, 6-3, 6-4 to give her team a 2-1 lead.
The French victory was especially sweet for Forget as it avenged last year's defeat to a Russian team led by his counterpart Shamil Tarpishchev in the Davis Cup final.
HEROINE RAYMOND
American Lisa Raymond had a role in the winning of three of her country's four points in the other semi-final against a weakened Belgium team playing without the world's top two players in Justine Henin-Hardenne
First, Raymond trounced Els Callens 6-2, 6-1 on Wednesday before crushing Clijsters' younger sister Elke by the same score in Thursday's action.
Within minutes of her second victory, Raymond was back on court in partnership with Martina Navratilova and the American pair crushed Clijsters and Caroline Maes 6-1, 6-4 in the dead doubles rubber to complete a 4-1 victory.
"I haven't played a singles match since 1999, so it felt really good to play two solid matches here," said Raymond.
Navratilova improved her Fed Cup record to 38-0 with Thursday's win.
"It's pretty amazing to be on a court with her," Raymond said "It's one thing to represent your country, but to do it with Martina is something else."
Navratilova, who at 47 played her first Fed Cup match since 1995 to become the oldest player in the competition's 40-year history, holds another record.
Navratilova, who won her first Fed Cup title with Czechoslovakia in 1975, has never played on a losing team.
"Yes, it's true, I have never lost in singles or doubles and in the old days we only played three matches instead of five," she said. "So by winning both of my matches, singles and doubles, I would guarantee my team of a win."
The Americans, also missing several of their top players, have won the Fed Cup a record 17 times.
The draw for the final, which takes place at the weekend, is at 1000 GMT on Friday.