The Belarussian, who claimed her maiden grand slam title in Melbourne 12 months ago, is the top seed and world number one but will fear the challenge of Serena Williams.
Olympic champion Williams, who also won Wimbledon and the US Open in a blistering end to 2012, will take on another Romanian Edina Gallovits-Hall first up.
Second seed Maria Sharapova meets fellow Russian Olga Puchkova.
Azarenka was forced to pull out of the warm-up event in Brisbane with a toe infection caused by a pedicure but she insists she is fully fit heading into the season's opening grand slam event.
She said: "It's much better. I have been practising for the last couple of days so I am really happy it's all gone and it's behind me."
Britain's two definite entries in the main draw were handed winnable opening matches.
Laura Robson takes on America's Melanie Oudin with a second-round meeting against either Francesca Schiavone or Petra Kvitova the reward for the winner.
Heather Watson was drawn against Romania's Alexandra Cadantu.