Serena Williams, Li Na in top half of Australian Open draw
Serena Williams of the US, seen in action during the Brisbane International tournament, on January 3, 2014
Williams, who could equal Martina Navratilova and Chris Evert's total of 18 Grand Slam singles titles with victory at Melbourne Park, will play Australian Ashleigh Barty first up.
The American, a five-time Australian Open champion, is seeded to face Italy's seventh seed Sara Errani in the quarters before a potential semi-final clash with fourth-seeded Li.
Li, who lost to Victoria Azarenka in last year's final, is drawn to face Czech left-hander Petra Kvitova in the last eight.
Two-time defending champion and world number two Azarenka will play Sweden's Johanna Larsson in the opening round and has a potential quarter-final with Polish fifth seed Agnieszka Radwanska.
Russian third seed Maria Sharapova, a winner in Melbourne in 2008, faces a tough opening round against American Bethanie Mattek-Sands.
Mattek-Sands upset top seed Radwanska at this week's Sydney International, but later withdrew from the tournament with back trouble.
Sharapova was seeded to face Serbian eight seed Jelena Jankovic in the quarter-finals.