The seven-time world champion beat Bai Langning 4-0, which included a break of 118 in frame two.
O'Sullivan reached three figures in three minutes and 34 seconds, which was just three seconds short of equalling the world-best set by Malta's Tony Drago 26 years ago.
Shaun Murphy was also in blistering form at Meadowbank Sports Centre in Edinburgh, hitting three centuries during a 4-0 stroll against Lei Peifan.
Murphy had breaks of 100, 104 and 107, amassing a total of 435 points in four frames, while his opponent managed just two.
Mark Selby also moved into round two with a 4-2 victory over Aaron Hill, while Neil Robertson beat Mark Davis 4-1.
There were no issues for Judd Trump and Mark Allen, as they posted comfortable victories, with Trump defeating Sanderson Lam 4-0 and newly-crowned UK champion Allen seeing off Andy Lee 4-1.
Jack Lisowski, meanwhile, was in dominant form, defeating Gerard Greene 4-1 after breaks of 105, 89 and 93 saw him reel off three frames in succession to close out the match, and Mark Williams and John Higgins also eased through.
But former world champion Stuart Bingham suffered a shock first-round defeat.
Bingham, who won the world title seven years ago, lost 4-3 to fellow Essex potter Zak Surety.
World number 97 Surety led 3-1 before Bingham recovered to set up a decider, but Surety compiled a brilliant break of 133 to claim an outstanding win.
And defending Scottish Open champion Luca Brecel also bowed out, losing 4-3 to Glaswegian Fraser Patrick.