If all goes according to plan for Williams she could face Caroline Wozniacki, whom she beat in the final of the 2014 US Open, in the quarter-finals and defending Wimbledon champion Petra Kvitova in the semi-finals.
In the bottom half of the draw, second seed Maria Sharapova will face a qualifier first up, with Eugenie Bouchard and Ana Ivanovic possible quarter-final and semi-final opponents respectively.
Third seed Simona Halep will have to negotiate her was passed Italian Karin Knapp in what could prove a tricky test for the Romanian.
Victoria Azarenka and Sloane Stephens will do battle in what is perhaps the tie of the opening round. The pair met in a controversial semi-final in 2013 where Azarenka's lengthy injury timeout saw her come in for heavy criticism from the Melbourne faithful.