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A repeat performance was not meant to be, as Clijsters was wide on match point to end any chance at becoming the eighth woman to repeat as Aussie champion.
Azarenka is 3-3 in her career against Sharapova, with two of those wins coming in finals.
The winner of Saturday's title match will become the new world No. 1, supplanting Clijsters' quarterfinal victim, Caroline Wozniacki. Sharapova has not held the top ranking since the week of June 8, 2007.
Kvitova beat Sharapova in straight sets to win her first Grand Slam last July, but trailed early against the three-time major titlist on Thursday at Melbourne Park.
Sharapova, seeded fourth, lost the second set, and was down 0-30 at 4-4 in the third before a replay reversal gave her new life. The Russian won the next four points to put the pressure back on Kvitova, who could not hold serve thanks to several unforced errors in the final game.
The 22-year-old Azarenka, meanwhile, became the first Belarusian woman to reach a Grand Slam final since Natasha Zvereva was the runner-up at Roland Garros in 1988 when she was representing the Soviet Union.
In doing so, Azarenka ended another memorable performance Down Under by Clijsters, who has stated she will retire after the Summer Olympics in London.
Clijsters, the 11th seed, quickly evened the match before falling behind 4-1 in the third. She held serve and trailed 40-0 in the next game before earning another break to get back on serve.
"I felt like my hand is about 200 kilograms and my body is about 1,000 and everything is shaking, but that feeling when you finally win is such a relief. My God I cannot believe it's over. I just want to cry," Azarenka said as she fought off tears, then put her face in a towel.
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