The 39-year-old eighth seed fell 7-6 (8/6), 7-5 in under
just two hours to the 44th-ranked Argentine, a surprise semi-finalist at last
year's Roland Garros.
Williams, a four-time Rome winner and 23-time Grand Slam
champion, had not played since her semi-final defeat in the Australian Open
this year.
The early exit is a blow three weeks before the French Open
in Paris on 30 May where the American continues her bid to equal Australia's
Margaret Court's record of 24 Grand Slam trophies.
Despite a battling performance, Williams could not wear down
the 24-year-old Argentine who broke the American twice in the first set.
In the second, Williams was trailing 5-2 but held and broke
the Argentine to love while she served for the match to level at 5-5.
Podoroska held her nerve to earn three match points to
secure just her third career win over a top-10 player, all in the last eight
months.
For Williams, it was her 149th defeat, with 851 wins over
the course of a WTA career covering 1000 matches.
But she will not get to celebrate with the Rome public, with
spectators only allowed from Thursday's third round at the Foro Italico while
limited to a 25 percent capacity.
Podoroska next meets Croatia's Petra Martic, who earlier
beat France's Kristina Mladenovic 7-5, 6-3.
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