Alcohols are reported to have superlubricity at low loads during sliding; however, their lubricity under high loads has rarely been reported. Meanwhile, the lubrication mechanism of alcohols under high loads is still not well understood. Here, we first report the lubricity of methanol under 98 N and 1450 rpm and demonstrate the formation of graphene and fullerene-like nanostructures induced by tribochemical reactions. Results show that the lubrication mechanism was mainly attributed to the friction-induced graphene under boundary lubrication condition. Besides that, the wear rate of a YG8 hard alloy ball mainly occurred at the run-in processes, and the friction-induced graphene effectively inhibited further wear after the run-in processes. The formation mechanism of graphene was well investigated, and the flash temperature rise and catalyst (WC, WO2, and WO3) were the major causes for the formation of graphene.