Investigations on adsorption behavior of triphenylene (TP) and subsequent graphene self-assembly on Cu(111) werecarried 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) sub-strate 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 Moir(e) pattes generated from relative ro-tational 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 Moir(e) supercell, and the third with 10?rotation with a periodicity of 1.35 nm.