Spectators boo losing Williams off court
The 18-year-old from Moscow defeated Williams 2-6, 6-2, 6-4 to break the domination of the most famous sister act in sport.
It means there will be no all-Williams final at a Grand Slam for the first time since the Australian Open in January 2002.
But there will be a Russian in the semi-final, after 20-year-old Nadia Petrova kept the seeds tumbling with an epic 3-6, 6-4, 6-3 triumph against Jennifer Capriati.
However, the behaviour of the spectators suggested the French crowd along with many other tennis fans believed it was a result which could only be good for the game.
In truth, Williams was a shadow of the woman who won back-to-back titles at Wimbledon and the US Open in 2000 and 2001. And Zvonareva took full advantage, scrambling for every point and exposing a flurry of errors on the Williams forehand.
Williams later insisted she was unconcerned with the hostile reception she received from a small section of the French fans at the end.
"I hope at least they had some entertainment today," said Williams. "I did what I could today. What else can I do? I'm very disappointed, I was just really off today."
Her sister Serena had a better day, staying on course to land her fifth successive Grand Slam by beating Japan's Ai Sugiyama 7-5, 6-3 and setting up a quarter-final against Frenchwoman Amelie Mauresmo.
Mauresmo had easily edged past Spain's Magui Serna 6-1, 6-2. The French number five seed later said she is in her best Grand Slam form ever.
Belgium's Justine Henin-Hardenne celebrated her 21st birthday with a 6-3, 2-6, 6-2 victory against Switzerland's Patty Schnyder.
In Tuesday's quarter-final, Henin-Hardenne plays America's Chanda Rubin, who struggled from a set down against Hungary's Petra Mandula 4-6, 6-2, 7-5.
Number two seed Kim Clijsters meanwhile was caught cold on such a hot day, losing the first set 6-0 before coming back to win the next two comfortably 6-2, 6-1 against Bulgaria's Magdalena Maleeva.
Clijsters now meets former Wimbledon champion Conchita Martinez, who got through courtesy of a foot nerve problem which forced sixth seed Lindsay Davenport to retire 2-0 down in the second set, having lost the first 6-4.
Andre Agassi as usual blew kisses to all four corners of Court Philippe Chatrier after taking his place in the men's quarter-finals.
There was presumably also one for his wife Steffi Graf, pregnant with their second child, who was attending this tournament for the first time to watch as he demolished Brazil's Flavio Saretta 6-2, 6-1, 7-5.
It was his 998th match on the ATP Tour, and as he closes in on the 1000th it seems that domesticity and fatherhood have replaced the wild tendencies he once experienced.
"I believe children help you to keep a lot of things in perspective," said Agassi. "It doesn't matter what day you're having, you go home and forget about it, whether it's a good day or a bad day. I think it helps with your balance."
Meanwhile, the unseeded Dutchman Martin Verkerk eased through to the quarters with a stunning 6-3, 6-3, 7-5 victory against eleventh seed Rainer Schuettler.
He will now play number four seed Carlos Moya from Spain, who defeated Jiri Novak 7-5, 6-3, 6-2.
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