The Belarusian, who has shown gritty brilliance and fragile doubt in equal measure throughout the tournament, got through a controversial semi-final against American teenager Sloane Stephens to reach her third Grand Slam final overall.
A seemingly-calculated medical timeout in the second set allowed Azarenka to regain her composure when it appeared to be slipping and close out the match in straight sets.
A further incentive for Azarenka is that only a victory in the final would see her stay at the top of the world rankings.
While there has been the usual flurry of controversy around the champion, Li Na has been a model of cool industry during her two weeks in Melbourne.
The histrionics of old have been left in the locker room with the Chinese sixth seed showing an all-round strength to her game that has allowed her to dismantle opponents, particularly Maria Sharapova in the semi-finals.
The 29-year-old, who is likely to have most of the crowd's support inside the Rod Laver Arena, will also be desperate to shake off the 'One-Slam Wonder' tag that has followed her for nearly two years since she won the French Open in 2011.
Azarenka 5-4 Li
Previous best at Australian Open:
Azarenka: Winner 2012
Li: Final 2011, 2013
Route to semi-finals:
R1: Monica Niculescu 6-1 6-4
R2: Eleni Daniilidou 6-1 6-0
R3: Jamie Hampton 6-4 4-6 6-2
R4: Elena Vesnina 6-1 6-1
QF: Svetlana Kuznetsova 7-5 6-1
SF: Sloane Stephens 6-1 6-4
R1: Sesil Karatantcheva 6-1 6-3
R2: Olga Govortsova 6-2 7-5
R3: Sorana Cirstea 6-4 6-1
R4: Julia Goerges 7-6(6) 6-1
QF: Agnieszka Radwanska 7-5 6-3
SF: Maria Sharapova 6-2 6-2
Sports Mole says: Li Na to taste Grand Slam glory again