The defeat by the 20th-ranked Svitolina ends Williams'
Olympic tournament, having also suffered a surprise loss in the
doubles with older sister Venus on Sunday.
The 34-year-old Williams, who is not entered in the mixed
doubles, cut short her media commitments after the loss,
speaking only to the official broadcasters before she returned
to the changing rooms.
Svitolina, who will face Czech Republic's Petra Kvitova in the
quarter-finals, was over the moon with her first victory in five
meetings over the 22-times grand slam singles winner.
"It's an unreal feeling for me. This is just a perfect moment,"
said Svitolina.
Williams grew increasingly frustrated during the match as she
struggled to find her range, making 37 unforced errors compared
to 17 by the 21-year-old Ukrainian.
Late in the second set, Williams served five double faults in a
single game, which drew gasps from a shocked audience.
She took out her frustrations on her racquet, slamming it into
the court surface on at least two occasions.
Williams' defeat came hours after third seed and French Open
champion Garbine Muguruza was upset by Puerto Rico's Monica
Puig.
Germany's world number two Angelique Kerber, who beat Williams
in the final of the Australian Open in January but lost the
Wimbledon final to the American, is now the favorite for gold.
Williams had won three doubles Olympic titles with Venus. Their
first round loss to Czech duo Barbora Strycova and Lucie
Safarova was their first Olympic loss in the doubles.
They won the title in Sydney, did not pair up for Athens due to
an injury to Serena but reclaimed the title in Beijing then
defended it in London.
They have also won 14 women's doubles grand slam titles.
(additional reporting by Alexandra Ulmer; Editing by Greg
Stutchbury)
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