Henin and Williams have met eight times in their careers but Saturday's clash will be the first since the muscular American won a semi-final meeting with the Belgian at Wimbledon nearly four years ago.
They needed iron willpower to stagger through scrappy quarter-finals on Wednesday and set up a heavyweight meeting in the last four.
The Russian overcame a groin injury to reach her first Kremlin Cup final beating Czech teenager Nicole Vaidisova.
Top seed Amelie Mauresmo joined Russian trio Elena Dementieva, Nadia Petrova and Anna Chakvetadze in the Kremlin Cup quarter-finals on Thursday.
Martina Hingis reached the final of the Montreal Cup after Anna Chakvetadze retired.
Second seed Maria Sharapova crushed defending champion Mary Pierce 6-2 6-3, setting up a last four clash with Patty Schnyder of Switzerland, who beat number four Elena Dementieva 6-4 6-3.
The Russian will meet Patty Schnyder, who beat number four Elena Dementieva, in the semi-finals of the Acura Classic.
However, the Indian ace and her partner South African Liezel Huber, entered the doubles quarter-finals of the Acura Classic.
Romanian teenager Sorana Cirstea upset third seed Anna Chakvetadze 6-2, 1-6, 6-2 in the second round of the Family Circle Cup.
The Indian ace and Anna Chakvetadze of Russia will take on Alina Jidkova of Russia and Tatiana Perebiynis of Ukraine in their opening match of the women's doubles at Wimbledon.
The Indian ace was pushed down by Russia's Anna Chakvetadze and Spain's Anabel Medina Garriques, who occupy the 32nd and 33rd places respectively.
The fine run at the WTA event in Stanford fetched the Indian ace 190 points and took her four rungs up.
Top seed Anna Chakvetadze defeated India's Sania Mirza 6-3, 6-2 to win her first Stanford classic title.
Lindsay Davenport beat Russian Anna Chakvetadze 6-3, 6-3 to reach the final of the New Haven Open
The American will regain the world number one ranking from Russian Maria Sharapova if she reaches the final.
Mirza teamed up with Russian Anna Chakvetadze to beat Kristina Brandi of Puerto Rico and Nana Miyagi of Japan.
The Indian ace lost 6-4, 6-1 to world number 13 Anna Chakvetadze in the semi-final of the WTA event in Hobart.
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