The 23-year-old Belarusian holds a 5-4 career record against former French Open champion Li, including the last four of their encounters.
Li, however, has prevailed in both their grand slam clashes, including her run to the 2011 final at Melbourne Park where she was overhauled by Belgian Kim Clijsters in three sets.
Both players are bidding for their second grand slam crown.
Top seed Azarenka has endured a turbulent leadup to the final, fending off accusations of gamesmanship in her 6-1 6-4 semi-final win over Sloane Stephens in which she took a near-10 minute medical timeout after blowing five match points.
Belarus's first grand slam singles champion denied the charge, however, saying she needed treatment for a rib injury that was affecting her breathing during the tense phase of the match.
Li has enjoyed a far smoother lead-in and will enter Rod Laver Arena brimful of confidence after demolishing Maria Sharapova 6-2 6-2 in their last-four clash.
Defeat for Azarenka would mean surrendering her world number one ranking to Serena Williams, while victory for Li would make the Chinese the oldest woman to win the singles trophy at Melbourne Park.
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