The 34-year-old tennis player and reigning Olympic champion lost 6-4 6-3 to Ukraine's Elina Svitolina.
Serena won the singles match at the London Olympics and she won the gold in the women’s doubles finals alongside sister Venus Williams in 2000, 2008, and 2012.
Venus lost in the opening round of the singles to Kirsten Flipkens while the sisters lost their first ever Olympic doubles match on Sunday.
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