Kim Clijsters will open the defence of her Australian Open title against a qualifier with Britain's Elena Baltacha a possible second-round opponent.
Thursday's draw in Melbourne placed Belgian Clijsters in a tricky quarter alongside Li Na - who she beat in last year's final - and world number one and top seed Caroline Wozniacki.
Baltacha takes on Stephanie Foretz Gacon first up.
Britain's Heather Watson takes on third seed Victoria Azarenka while Anne Keothavong meets Mona Barthel.
Wozniacki, whose place at the top of the rankings was guaranteed for a little longer after Petra Kvitova's defeat to Li in the semi-finals in Sydney on Wednesday, opens against Anastasia Rodionova although a last-eight clash with Clijsters looms large.
Wozniacki injured her wrist during her quarter-final loss to Agnieszka Radwanska in Sydney but expects to be fit for Melbourne.
Serena Williams, a winner of 13-grand slam crowns, was paired with Tamira Paszek in the opening round and could meet fourth-seeded Russian Maria Sharapova in the quarters.
2011 US Open champion and home favourite Samantha Stosur meets Sorana Cirstea in her first match after being placed in the same quarter as Kvitova, who opens with a clash against Russia's Vera Dushevina.