The 36-year-old teamed up with Rajeev Ram to beat India’s Sania Mirza and Rohan Bopanna 2-6, 6-2, 10-3 in the semi-final. Britain’s Kathleen McKane also won five medals between 1920-24.
On Sunday, Venus also bids to become the first ever tennis player to win five Olympic gold medals. She currently shares the record of four golds with her sister Serena.
“I’m used to doing this with Serena and it’s such a crazy feeling to do it with someone else,” said Venus who was beaten in the first round of the singles in Rio as well as the doubles with Serena.
“To feel what I feel with Serena, (but) with someone else, is a wild emotion and I never thought it would happen.”
Williams and Ram will face fellow Americans Bethanie Mattek-Sands and Jack Sock who beat Lucie Hradecka and Radek Stepanek 6-4, 7-6 (7/3).
Williams said she was stunned to be in gold medal match as she and Ram were only teamed together at the last minute.
“It’s different. With Serena, I expect to win, I got to be honest. And we (Ram) never play together, and we didn’t know how we were going to play,” she explained.
“So the emotion is almost even bigger because you don’t know what to expect.”