The three-times Wimbledon champion will partner Taylor Dent for the United States at the Dec. 29-Jan. 5 event in Perth's Burswood Dome.
Dent partnered Lisa Raymond to win the last Hopman Cup but tournament director Paul McNamee deviated from the normal policy of inviting the defending champions back to accommodate the five-times grand slam champion.
"We love to showcase new faces and exciting talent and Venus is one of the stars of the game that hasn't been here yet," McNamee said in a statement.
"She is back on the WTA Tour and in good form so I thought I would see if she would like to partner Taylor. Venus becomes the 19th number one to have played in 19 Hopman Cups, which exemplifies the quality of this event."
Reigning Wimbledon champion, Venus also won the grasscourt grand slam in 2000 and 2001, the same years she won the U.S. Open.
Venus follows in the footsteps of younger sister Serena who won the Hopman Cup partnering James Blake in the 2002-2003 event.
