Former No. 1-ranked Jankovic had lost three of her four previous matches against Pavlyuchenkova and didn't start well in Beijing, but recovered to earn three service breaks in each of the second and third sets in a dominating finish.
Jankovic's compatriots Ana Ivanovic and Bojana Jovanovski joined her in the second round with easier straight-set victories.
In the doubles, wildcard entrants Serena and Venus Williams wasted chances to win before losing 6-7 (3), 6-4, 11-9 to Liezel Huber and Taiwan's Chan Hao-ching.
In the men's draw, Australia's Bernard Tomic opened with a 7-6 (4), 6-4 win over local challenger Zheng Ze.
Results from the China Open in Beijing on Monday (x denotes seeding):
Bernard Tomic (AUS) bt Zhang Ze (CHN) 7-6 (7/4), 6-4
Fabio Fognini (ITA) bt Tommy Robredo (ESP) 7-5, 4-6, 6-3
Roberto Bautista Agut (ESP) bt Grigor Dimitrov (BUL) 6-4, 6-2
Philipp Kohlschreiber (GER) bt Albert Montanes (ESP) 7-5, 1-6, 7-6 (7/4)
Lleyton Hewitt (AUS) bt Tommy Haas (GER x7) 7-6 (8/6), 6-3
Ana Ivanovic (SRB x14) bt Flavia Pennetta (ITA) 7-6 (11/9), 6-1
Jelana Jankovic (SRB x8) bt Anastasia Pavlyuchenkova (RUS) 1-6, 6-4, 6-0
Bojana Jovanovski (SRB) bt Sorana Cirstea (ROM) 6-3, 6-2
Eugenie Bouchard (CAN) bt Magdalena Rybarikova (SVK) 6-4, 6-1
Galina Voskoboeva (KAZ) bt Sharon Fichman (CAN) 6-4, 6-3
Svetlana Kuznetsova (RUS) bt Hsieh Su-Wei (TPE) 6-1, 6-1
Zhang Shuai (CHN) bt Peng Shuai (CHN) 6-3, 6-3
Andrea Petkovic (GER) bt Victoria Azarenka (BLR x2) 6-4, 2-6, 6-4
Polona Hercog (SLO) bt Monica Puig (PUR) 6-1, 6-4
Sara Errani (ITA x5) bt Misaki Doi (JPN) 6-3, 6-2
Lucie Safarova (CZE) bt Kaia Kanepi (EST) 6-3, 6-3