A poor finish to Saturday's third round had left Rose three behind Li at the start of the day but a front nine of 33 and a birdie at the 10th, which he had bogeyed in the previous two rounds, was enough for a share of the lead.
Both players returned to the 18th for the playoff and after Rose missed a 15-footer for birdie, Li surprisingly three-putted from just nine yards to hand his opponent the title.
"I think I played well the whole week but didn't hole a few putts on the last and that was it".
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Late charges from the likes of Martin Kaymer, Lucas Bjerregaard and Danny Willett ultimately came up short as the top two went head-to-head down the stretch, with Alex Levy out of the running after four bogeys over a wretched first 10 holes.
Li sits in first at 17 under through 54 holes at Regnum Carya Golf and Spa Resort.
In truth, this play-off triumph over the 23-year-old Chinese Haotong Li was hardly a thing of beauty, regardless of the riches it reaped, which included a cheque for more than £900,000.
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Rose struck what looked like the killer blow with a birdie on the 14th, but Li responded with a stunning approach to the par-5 15th to set up a tap-in eagle as Rose three-putted from long range for par. Rose would return to No. 1 in the world with a victory.
However, it was Li's turn to three-putt from long range and Rose was left with a putt for the win after a superb bunker shot, only to miss from four feet.
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First the young Tottenham defender fouled Raul Jimenez, with Ruben Neves converting from the spot in the 68th minute. Sometimes to win titles today is hard , for many reasons that you and our fans know very well.