The Serbian third seed, who beat Federer in the semi-finals of the 2008 Australian Open and went on to win the major, is in line for a semi-final with second seed Federer on seeding projections.
World number one Rafael Nadal has Sweden's fourth seed Robin Soderling and last year's beaten finalist and fifth seed Andy Murray of Great Britain in his top half of the draw.
Nadal, who won the French Open, Wimbledon and the US Open last year to complete a career Grand Slam at the age of 24, opens the Melbourne tournament against Brazil's Marcos Daniel.
Federer has a first-round match against Slovakia's Lukas Lacko, while Djokovic lines up against Spaniard Marcel Granollers and Murray faces Slovakian Karol Beck.
Soderling, who was runner-up to Nadal at last year's French Open, has Italian Potito Starace first up.
The intriguing first-round matchup is between two-time major winner Lleyton Hewitt and Argentina 27th seed David Nalbandian, who the unseeded Australian defeated in the 2002 Wimbledon final.
Argentina's unseeded Juan Martin del Potro, who beat Federer to win the 2009 US Open final and fighting back from a wrist injury, takes on Israeli Dudi Sela in the first round.
The season's opening Grand Slam tournament gets under way at Melbourne Park on Monday.