The five-time Wimbledon singles title winner, who has battled injuries and entered the tournament as a wild card, was defeated by the Ukrainian Elina Svitolina in two sets.
Svitolina was playing out her own story of resilience, returning to Wimbledon after the birth of her daughter in October.
Williams was greeted with cheers and adoration as she took to the court, with the crowd delighted to welcome the seven-time grand slam singles champion back to SW19.
In a close first set that took more than an hour, Williams slipped and fell and was broken by Svitolina, before going on to lose 4-6.
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