Russia, the hot favourites, had Myskina to thank for a nervy 3-2 victory in the final which underlines the country's domination of the women's game.
The French Open champion gave the home team all three points by winning both her singles matches before teaming up with Zvonareva to beat Emilie Loit and Marion Bartoli 7-6, 7-5.
The two nations were level at 2-2 after Tatiana Golovin kept alive France's hopes of retaining the title by crushing U.S. Open champion Svetlana Kuznetsova 6-4, 6-1 in the second reverse singles.
Myskina had put the home team ahead 2-1 when she eased past Nathalie Dechy 6-3, 6-4.
Russia captain Shamil Tarpishchev chose to replace doubles specialist Elena Likhovtseva with Myskina for the decider and his gamble paid off as it was the world number three who looked the much steadier of the four players.
GREAT FEELING
The Russians saved four set points and then survived a tense tiebreaker to clinch the first set before wrapping up the match and the overall victory after two hours 13 minutes.
"It's a great feeling to lead your team, your country to victory," said Myskina, who this year became the first Russian woman to win a grand slam title when she beat compatriot Elena Dementieva in the French Open final.
"For me it's a lot more satisfying than any individual achievements I've had before."
Tarpishchev, who also guided Russia to their first Davis Cup title with a comeback 3-2 win over holders France two years ago in Paris, said he felt relief.
"It's hard to measure happiness so I don't know which of the two wins is more satisfying,
For Guy Forget, who captained France to their second Fed Cup title a year ago in Moscow, it was a painful defeat.
"I have to say the best team won," said the Frenchman, who gave his team only a "small chance" to win before the final.
"For us to win we had to play three extraordinary matches and we only had two. Of course, it's more painful to lose when you come that close."
NO REGRETS
The Russians had been overwhelming favourites to capture their first title on home soil against a French team missing world number two Amelie Mauresmo and twice Grand Slam champion Mary Pierce, but Forget had no regrets.
"Well, we didn't have both Amelie and Mary here and I'm not sure if Russia would have won without Myskina and Kuznetsova, but we just have to accept this," he said.
"I'm very proud of all the French girls. They did the best they could."
Moscow-born 16-year-old Golovin was in tears when she showed up for a post-match news conference.
"Of course, we're all very dissapointed, almost heart-broken," said the French teenager, who made her Fed Cup singles debut this week.
"Personally for me, I've learnt a lot this week and beating Kuznetsova here in Moscow was just fantastic," said Golovin, who left Russia when she was eight months old.
"It was my first win against such a high-ranked player but I know I can play a lot better," she added after being told that world number five Kuznetsova described her performance in their match as "above her head".
As well as the Fed Cup title and Grand Slam triumphs for Myskina and Kuznetsova, Russia's Maria Sharapova was crowned Wimbledon champion in July.