Investigations on adsorption behavior of triphenylene (TP) and subsequent graphene self-assembly on Cu(111) were carried out mainly by using scanning tunneling microscopy (STM). At monolayer coverage, TP molecules formed a long-range ordered adsorption structure on Cu(111) with an uniform orientation. Graphene self-assembly on the Cu(111) substrate with TP molecules as precursor was achieved by annealing the sample, and a large-scale graphene overlayer was successfully captured after the sample annealing up to 1000 K. Three different Moiré patterns generated from relative rotational disorders between the graphene overlayer and the Cu(111) substrate were observed, one with 4° rotation between the graphene overlayer and the Cu(111) substrate with a periodicity of 2.93 nm, another with 7° rotation and 2.15 nm of the size of the Moiré supercell, and the third with 10° rotation with a periodicity of 1.35 nm.