Bustamante, ranked second to compatriot Efren "Bata" Reyes in the three-day event which stakes $10,000 to the winner, took three of the first four racks then went on to beat Chu Hung-Ming of Chinese-Taipei, 9-5, at the Hanggar Billiard and Recreation Center.
That victory set up a clash with Valle, winner of the kickoff leg in Singapore who romped away with a 9-2 rout over Hong Kongs Au Siu Wai.
Bustamante and Valle, grouped in the lower bracket, were battling it out in the Last 16 at presstime.
"Ganyan talaga ang draw," said Bustamante, who defeated Valle, 11-4, in the semifinals on the way to the title in the recent All-Filipino Open. "Siyempre mabigat dahil Pilipino ang kalaban, kaya kung sino ang buwenasin yun na ang panalo."
Lee Van Corteza, however, got the boot as he was ousted by two-leg winner Yang Chin-Shun of Chinese-Taipei, who rallied from a 0-5 deficit to complete a big 9-6 victory.
Winner of the Tours Manila leg last year, Corteza settled for $750.
Fresh off a victory in the Japan Open two weeks ago, Reyes was to play fellow former world champ Kunihiko Takahashi, while Roberto Gomez Jr., a qualifier who took the place of first-leg semifinalist Antonio "Gaga" Gabica, was to open his campaign against Taiwans Kuo Po-Cheng, both at presstime.
Two seeded players were also upset.
No. 3 Korean Jeong Young Hwa was upended by Singapores Toh Lian-Han, 5-9, and Chinas Xu Meng stunned off No. 7 Patrick Ooi of Malaysia by the same score.
Third seed Chao Fong Pang had some difficulty disposing of the hosts Yudarman Kamarudin, 9-7, but still arranged a second-round duel with fellow Taiwanese Wu Chia Ching, who edged Singapores Chan Keng Kwang, 9-7.
Japans Satoshi Kawabata, the No. 6 seed, breezed past Thailands Chatchawan Ruthpae, 9-2, to set a second-round encounter with Chinas Li He-Wen, a 9-7 winner over Tran Quang Trung.
Indonesia got a win courtesy of Muhammad Zulkifri, who beat Malaysias Ibrahim Bin Amir, 9-5, to set a duel with the Singaporean Toh. Thailands Wanshana Poomjaeng also went through, whipping Koreas Ham Won Sik, 9-2.