The WTA event is the first tournament organised by the association since the suspension of competitive tennis due to the coronavirus pandemic.
Williams looks as though she might fall at the hands of her own rustiness as she went down 6-4 in the first set as she prepared for the upcoming US Open.
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Murray set to practice with Djokovic in Rome ahead of latest comeback
However she fought back to break her opponent in the last game of the second set to level at one set each.
The next set was far more comfortable as the 38-year-old former world number one won at a canter, six frames to one.
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