In her fifth Olympics, it just wasn't meant to be for Venus Williams.

The 36-year-old suffered an opening-round loss to Belgian Kristen Flipkens, 4-6, 6-3, 7-6 (7-5) at the 2016 Rio Olympics.

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Venus Williams was eliminated from the singles tournament at the Rio Olympics. Getty Images

Williams looked to be in control after a win in the first set, but fatigue started to set in as the 30-year-old Flipkens won the second set before winning the final set in a tiebreaker.

Flipkens came into the Olympics ranked No. 62 in the world, while Williams was ranked No. 6.

Williams will still have a chance for gold in doubles, partnered with her sister Serena. They begin doubles play on Sunday.