It appeared the world number one had a shoulder problem and was close to tears as she lost 6-4 6-3.
Meanwhile, the Williams sister have been the most successful players in Olympic tennis history with each of them claiming four Gold medals but Rio 2016 has not gone according to plan.
Venus Williams lost in the opening round of the singles to Kirsten Flipkens while the sisters lost their first ever Olympic doubles match on Sunday.
It seems it's not their year this time around or maybe age is telling on them.
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