Li set up a final with compatriot Ding Ning in the women's Singles.
The nation has thus far claimed more top prizes than anyone else at the Games, with Table Tennis always likely to add to their haul.
Some expect they will claim the four golds available - something that looks all the more realistic now.
Much like her compatriot Ding, Li has encountered few problems in reaching Wednesday's final and had too much for Japan's Kasumi Ishikawa.
It means whatever happens China will continue their astonishing record of claiming every women's Singles medal since the sport was added to the Olympics schedule at Seoul 1988.
Ding was favoured before the event to win, but Li will no doubt be confident following her dominant effort today.
While her compatriot was challenged by Feng Tianwei of Singapore, eventually winning 4-2, Li was in charge for much of her 4-1 triumph against Ishikawa.
In the men's competition, Taiwan's Chuang Chih-Yuan admitted he had mixed emotions after overcoming best friend Adrian Crisan.
Chuang and Romanian Crisan share a bond off the table, but met on it for a place in the last four of the Singles at the ExCeL Arena.
Despite the attachment, Chuang was ruthless as he dominated Crisan, who pulled off a shock yesterday night by knocking out fourth seed Timo Boll.
Indeed, Chuang was in charge throughout, wrapping up a straight-games victory in just 20 minutes.
'He is my best friend,' said Chuang afterwards. 'I was sorry when I played him.'
Germany's Dimitrij Ovtcharov and Denmark's Michael Maze then battled out a seven-game thriller.
The former looked comfortable in moving into a 2-0 lead, with his opponent being yellow carded at one stage for showing his frustration.
However, Maze composed himself and, playing with extra power, reaped rewards from forcing the German on to his backhand to level matters.
They then took a game apiece, after which Ovtcharov edged the decider 11-9, much to the dismay of Maze's legion of fans.
Half of the quarter-final games were completed, with Chinese stars Zhang Jike and Wang Hao in action tomorrow morning.