Four years after Williams was booed off court following an acrimonious semifinal with the Belgian, the duo will face each other across the net at Roland Garros for the first time since then.
Australian Open champion Williams was the first to book her place in the last eight, darting past Russian Dinara Safina 6-2, 6-3.
Three hours later, Henin ousted Austrian Sybille Bammer in a ruthless 6-2, 6-4 exhibition.
Late in the evening, world number two Maria Sharapova survived two match points before overcoming Switzerland's Patty Schnyder 3-6, 6-4, 9-7 in a gripping match.
Schnyder served for the match three times before dropping serve in the last game, bowing out by sending a forehand wide after two hours and 37 minutes of a tight contest that could have gone either way.
Majestic Federer
Roger Federer's charge towards an elusive French Open title gathered momentum as he silenced roaring Russian Mikhail Youzhny 7-6, 6-4, 6-4. Next up for the world number one will be ninth seed Tommy Robredo.
The Swiss maestro, who is bidding to become only the third man to win all four majors in a row, has now won a record-equalling 35 successive sets at Grand Slams dating back to his triumph at the 2006 US Open.
For once Federer's majestic performance was not the talking point amongst Parisians. It was the forthcoming showdown between Henin and Williams that had tongues wagging.
Williams was left an emotional wreck after her reign as champion was ended in 2003 by Henin and she went on to accuse the Belgian of ‘lying and fabricating’ following a controversial point in the match.
Despite the passage of time, some things can never be forgotten. "I wasn't at fault in any way and I guess she was doing everything to win. Who knows? I don't know," said eighth seed Williams.
Serbian charge
While Williams was the only American left standing out of the 10 who had entered the women's draw, Jelena Jankovic and Ana Ivanovic highlighted the changing boundaries in the global tennis map.
They were the only Serbs to enter the field and remained on course for a final date.
Before she can look that far ahead, Ivanovic will have to overcome 2006 runner-up Svetlana Kuznetsova. The Russian foiled Shahar Peer's bid to become the first Israeli woman to reach the Paris quarterfinals with a brisk 6-4, 6-3 victory.
Fourth seed Jankovic ended French interest with a brutal 6-1, 6-1 thrashing of Marion Bartoli and will take on Nicole Vaidisova.
Davydenko wins
Russian Nikolay Davydenko chose the perfect time to snap a run of four straight defeats by David Nalbandian, edging through a punishing contest 6-3, 7-6, 3-6, 7-6.
The fourth seed, beaten by Nalbandian at the quarterfinal stage last year, withstood a superb fightback by the Argentine, underlining his tag as one of the most consistent performers on the men's circuit by reaching his fifth quarterfinal in his last six Slams.
Sania’s event over
Leander Paes and Meghann Shaughnessy survived a scare but Sania Mirza and Fabrice Santoro were knocked out of the mixed doubles, reports PTI.
Paes and American Sha-ughnessy managed to beat Marcin Matkowski of Pol-and and Sybille Bammer of Austria 6-2, 0-6, 10-8 to advance to the quarterfinals.
Sania and Santoro were put out by Katernia Srebotnik of Slovakia and Nenad Zimonjic of Serbia 6-2, 7-6 (7-1).
FRENCH OPEN RESULTS
Fourth-round results (prefix denotes seeding):
Men’s singles: 4-Nikolay Davydenko (Rus) bt 15-David Nalbandian (Arg) 6-3, 7-6 (7-1), 3-6, 7-6 (7-2); 1-Roger Federer (Sui) bt 13-Mikhail Youzhny (Rus) 7-6 (7-3), 6-4, 6-4; 9-Tommy Robredo (Spa) bt 29-Filippo Volandri (Ita) 6-2, 7-5, 6-1; 19-Guillermo Canas (Arg) bt Juan Monaco (Arg) 6-0, 6-4, 6-2.
Women’s singles: 2-Maria Sha-rapova (Rus) bt 14-Patty Schnyder (Sui) 3-6, 6-4, 9-7; 4-Jelena Jank-ovic (Ser) bt 18-Marion Bartoli (Fra) 6-1, 6-1; 7-Ana Ivanovic (Ser) bt 24-Anabel Medina (Spa) 6-3, 3-6, 6-3; 1-Justine Henin (Bel) bt 20-Sybille Bammer (Aut) 6-2, 6-4; 8-Serena Williams (US) bt 10-Dinara Safina (Rus) 6-2, 6-3; 6-Nicole Vaidisova (Cze) bt 19-Tathiana Garbin (Ita) 6-3, 6-1; 3-Svetlana Kuznetsova (Rus) bt 15-Shahar Peer (Isr) 6-4, 6-3; 9-Anna Chakvetadze (Rus) bt 25-Lucie Safarova (Cze) 6-4, 0-6, 6-2.