Ferrari was the Red Bull driver's nearest rival, with Felipe Massa just 0.078 seconds away in second place and Fernando Alonso third.
Lewis Hamilton took an encouraging fourth for Mercedes.
Local boy Daniel Ricciardo had the honour of being the first man on track in an official F1 2013 session, and also set the year's first flying lap with a 1m36.089s. Nearly 40 minutes elapsed between those achievements, as teams waited in the pits after their installation laps in the hope that others would clear the dust from the circuit.
Ricciardo battled for the top spot with Toro Rosso team-mate Jean-Eric Vergne for a while before the leading teams began setting the pace.
Lotus's Kimi Raikkonen was the first of the big guns to show his hand, eventually working down to a 1m27.877s. Alonso beat that mark by 0.3s five minutes later.
Vettel did not start chasing lap times until the final half an hour, ultimately deposing Alonso with a 1m27.320s.
Ferrari fought back as Massa edged ahead by 0.031s, but the Brazilian's time in first place was fleeting, as Vettel immediately improved to 1m27.211s.
That kept him on top to the end. The Ferraris remained in second and third ahead of Hamilton.
Mark Webber and Raikkonen rounded out the top six, with Nico Rosberg seventh in the second Mercedes.
Adrian Sutil's F1 comeback began well in eighth. Jenson Button, in ninth, was split from McLaren team-mate Sergio Perez by Romain Grosjean's Lotus.
Several drivers, particularly those in the tail-end cars, skittered across the grass and run-off areas.
The only incident of significance came in the final moments, when Paul di Resta brushed the grass on the approach to Turn 5 and spun his Force India sideways into the gravel trap, from which he was surprisingly able to haul himself out.