The world's top two players reached the final in contrasting fashion today, with Sharapova battling for two hours and 10 minutes to see off Victoria Azarenka 6-1 2-6 6-4.
Williams, meanwhile, routed last year's runner-up Sara Errani 6-0 6-1 in only 46 minutes to reach her first final at Roland Garros since she won her only title in 2002.
The last time Sharapova beat Williams was at the end-of-season WTA Tour Championships in 2004, since when they have met 12 times with the American winning the lot.
Sharapova has managed three sets in that time, including the first set of the Miami final in March, but Williams won their most recent match in Madrid last month 6-1 6-4.
Sharapova said with a smile: "I'd be lying if I said it doesn't bother me, obviously.
"I don't think that it would be a pretty competitive statement if I said it didn't. I would love to change that around.
"Obviously whatever I did in the past hasn't worked, so I'll have to try to do something different and hopefully it will. I'm proud of the way that I came through this tournament. I have given myself a chance to face the favourite."
Sharapova played very well in spells on Thursday against third seed Azarenka, who has been in fine form in Paris and held a 7-5 head-to-head advantage over the Russian.
After dropping the first game of the match with two double faults, Sharapova blitzed her way through six successive games and wrapped up the set with an ace.
But Azarenka is a fighter and she dug in at the start of the set before Sharapova started to miss and levelled the match as rain began to fall.
A break of just over half an hour helped the champion regain the ascendancy, but she missed four chances to serve out the match at 5-2.
Azarenka held to pile the pressure on but Sharapova made no mistake second time around, clinching victory with her 12th ace - one more than her tally of double faults.
The second seed said: "After having the momentum and leading 5-2, the last few points of the match are obviously the toughest in a stage like that.
"So, despite having those match points and not taking advantage of them, I was happy with the way I came out at 5-4 and served it out. That was really important."
The 26-year-old has transformed herself from a player who was completely uncomfortable on clay to one of the best in the world on the surface and she is delighted to be back in the final.
"I had a tremendous year last year here," said Sharapova. "Obviously to come back as the defending champion, it's extremely special to get back on that stage where it comes down to the last two players of the tournament.
"I'm happy from where I was in the beginning of the tournament to where I am today [Thursay]. I just hope that I can improve for the next one."
Williams has been in awesome form, winning 30 straight matches and 73 from 76 since losing in the first round here last year, but rarely has she been so dominant as she was on Thursday.
It was a mismatch in terms of power and it showed from the first point. Errani won just 16 points in the whole match, and held her arms aloft after finally getting on the scoreboard in the 10th game.
Williams was in no mood to be charitable, and she said: "I definitely can't allow myself (to feel for Errani).
"She's a great girl. I really, really like her. I love her fighting spirit. I really like her as a person. But when you go out there, you just have to play and forget about who you're playing."
It was Errani's heaviest defeat at the hands of Williams, but she insisted it was not an unpleasant experience.
Errani said: "I enjoyed playing today, really. It was a great court, great weather, great everything. What she did today is unbelievable. She's very strong. She's an unbelievable player. She had a great day. I tried."
Azarenka, meanwhile, has improved markedly on clay this year and was playing in her first semi-final at Roland Garros.
She said: "Today [Thursday] I'm disappointed about the match and what happened out there, but overall I have to give myself credit for going one step further.
"Even though I lost today [Thursday], I still tried to come back and tried to make something happen, which before was much more difficult for me to do.
"So this French Open is definitely the best one so far for me. But I have to keep working hard, and right now I just want to forget it."