Former world number one Victoria Azarenka has been knocked out of Wimbledon, losing 6-3 3-6 7-5 to Serb world No.45 Bojana Jovanovski.
Azarenka, twice a Wimbledon semi-finalist, had only returned to action at Eastbourne last week following a three-month lay-off caused by a left foot injury.
The 22-year-old Jovanovski has reached the third round for the first time and will next face Czech qualifier Tereza Smitkova.
Australian Open champion Li Na, a three-time quarter-finalist, swept to a 6-2 6-2 victory over Austria's Yvonne Meusburger, hitting 33 winners to just four from the world No.38.
Second seed Li, 32, goes on to face Barbora Zahlavova Strycova of the Czech Republic.
She says she's unconcerned about her 21 unforced errors.
"If you want to play more aggressive, this is the normal way," she explained.
Five-time champion Venus Williams, 34, and playing in her 17th Wimbledon, defeated pint-sized Japanese Kurumi Nara 7-6 (7/4) 6-1 in a battle of little and large on Court 3.
The American, who is the oldest woman left in the draw, stands at an imposing 1.85m (6ft 1in) compared to Nara's 1.55m (5ft 1n) and the difference in stature - both physical and sporting - eventually told despite the world No.41 breaking early in both sets.
Williams will now face 2011 champion Petra Kvitova in the third round.
"Feeling good getting into the next round," said Williams on Wednesday.
"I think we both play a similar game, really go for it and she's one of the kind of players that can get really hot and every time she plays me. She plays really well, so I have to be ready for that."
Polish fourth seed Agnieszka Radwanska, the 2012 runner-up, also went through with a 6-4 6-0 win over Australia's Casey Dellacqua and next meets either Portuguese qualifier Michelle Larcher de Brito or Australia's Jarmila Gajdosova.
Meanwhile, 1997 singles champion Martina Hingis appears at the All England Club for the first time since 2007 when she teams up with Russia's Vera Zvonareva in the women's doubles first round.
Hingis won nine grand slam doubles titles in her career but she and Zvonareva have a tough opener against fourth seeds Cara Black and Sania Mirza.
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