Australian Pilkadaris, who won last week's inaugural Shanghai Open, took a three-stroke lead into the final round and finished with a 2-under-par 70 and a 270 total.
Devers shot a 7-under-par 65 to force the playoff at the 6,487-meter (7,097-yard) Yalong Bay Golf Club on southern Hainan island.
'It's mind-blowing, unbelievable really,' Pilkadaris said of the win, adding that having his wife and caddie Monique with him made the achievement even sweeter.
'She wasn't with me when I won in Shanghai so I was more determined to get over the line today with her,' he said. 'She's like my rock and I'm glad we did it.'
Devers said that while he 'played good,' he wasn't happy with his two drives in the playoff.
'I left myself yardages that I'm not used to,' he said. 'After finding the bunker on the second playoff hole, I took out an extra club after seeing Terry hit it so close. He just gets it on the fairway and gets it on the green.'
China's Liang Wenchong could have made it a three-way playoff, but missed a 15-foot birdie attempt at the last hole in his round of 67. He shared third place with Thai veteran Boonchu Ruangkit, who played his second straight top-three performance.
In the closing stretch, Boonchu missed birdie chances from 4 feet and 10 feet on the 16th and 17th holes. He rolled in a birdie on the 18th to tie with Liang.
Pilkadaris nearly wrapped it up on the first hole of sudden-death but his 20-foot attempt hit the edge of the cup. He also struck a shot in the second extra hole from 170 yards that nearly found the bottom of the cup.
'It was near perfection,' he said.
Sri Lankan Anura Rohana fired a 68 to finish tied fifth on 273 for his best outing on the Asian Tour, alongside Taiwan's Chang Tse-peng, who closed with a 70.
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