US Fed Cup captain Mary Joe Fernandez announced the team today with world number 42 Christina McHale and Liezel Huber, world ranked number one in the doubles, joining the Williams sisters.
Seven-time grand slam champion Venus has not played in a competitive match since pulling out of the US Open in August last year after being diagnosed with Sjogren's Syndrome, an auto-immune disease.
For sister Serena, who went out of the Australian Open earlier this week following a fourth-round loss to Ekaterina Makarova, it will be her first Fed Cup appearance in almost five years.
The Belarus team are set to feature world number three Victoria Azarenka who will play Kim Clijsters tomorrow in the semi-finals in Melbourne.
The match will be held February 4-5 in Worcester, Massachusetts, with the winner progressing to the World Group playoff and a chance to compete for the Fed Cup title in 2013.