As for Puig, she is next scheduled to square off against local hope Qiang Wang on Thursday.
Barty, ranked number 17 in the world by the Women's Tennis Association (WTA), squandered the opportunity to seal the victory in the second set, when she was just two points from the win, and rallied later on to win the third set 6-4.
Wozniacki, the No. 2 seed, however, couldn't really get going as she stumbled to a stunning 6-7 (10) 5-7 defeat to her opponent from Puerto Rico, who came all the way from the qualifiers.
As Puig broke again to take a 4-3 lead, she would even begin to deploy a strategy of judicious net play to excellent effect, bringing the former World No.1 in with a dropshot before putting her own volley away, and more exquisite net play paved the way to another break for 6-5.
Kerber managed to level the set at five games apiece, before Barty reimposed herself on proceedings, winning eight of the last nine games to close out the second set and the match.
Wozniacki lost to Olympic champion Monica Puig 7-6 (10), 7-5, while Wimbledon champion Kerber was upset by Ashleigh Barty 7-5, 6-1. She also grabbed headlines at the French Open with her straight-sets demolition of Venus Williams.
Meghan Markle and Prince Harry spotted taking public transit to royal event
But her simple gesture sparked a huge debate on social media about whether she broke royal protocol by closing her own auto door. Ah, yes - everyone loves a royal rebel ignoring the rule book. "The work that they did here is just so lovely ".
Barty started strongly against the 39th-ranked Pavlyuchenkova, taking the first set 6-2, but the Russian did not appear in a mood to give in too easily and made an aggressive recovery to take the second.
Earlier, Australia's Ashleigh Barty had to dig deep to overcome Anastasia Pavlyuchenkova, beating the Russian 6-2, 5-7, 6-4 to secure her semi-final berth.
A tournament victory in China would take Barty, now No.17 in the world, to a projected career high of No.15 and above Serena Williams.
Wozniacki, this year's Australian Open victor, will face reigning Olympic champion Monica Puig.
The 22-year-old Barty said she is looking to sustain that momentum to end 2018 on "the best note possible, whether that is results-based or feelings-based".
But it was a short-lived fightback as Barty, Australia's top-ranked player, quickly regained control while Kerber struggled to contain unforced errors.
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