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We report an atomic scale investigation of growth mechanism and direct observation of growth intermediates for CVD graphene on Cu(111) under ultrahigh vacuum condition using methane as precursor,by in-situ low-temperature scanning tunneling microscopy (LT-STM),and corroborated by density-functional theory (DFT) calculations.It is found that methane molecules first decompose on Cu(111) surface and form carbon dimers (C2Hx),and various larger carbon clusters comprising carbon chains and square.