White pushed his Pedigree Mitsubishi Lancer Evo 10 into the lead past the identical car of Jason Bargwanna on lap 16 as daylight came to a damp but drying circuit.
Bargwanna's Pro-Duct teammate Glenn Seton was third.
Several incidents marked the first hour.
Queenslander Klark Quinn spun into a tyre wall going up the mountain when his Mitsubishi Lancer Evo 9 had brake problems. The car was being repaired but Quinn said his VIP team was already out of contention.
The Armor All Bathurst 12 Hour, in its fourth year as the ultimate test of showroom-standard production cars, is Australia's longest motor race. The winning car is expected to complete around 1500 kilometres when it crosses the line at 6.30 pm.
TOP THREE (7.30 am)
1 Car 1# Damien White, Mitsubishi Lancer Evo 10, 17 Laps 2 33# Jason Bargwanna, Mitsubishi Lancer Evo 10, 17 laps 3 35# Glenn Seton, Mitsubishi Lancer Evo 10, 17 laps
-source: bathurst 12h