Controlling the number of graphene layers is crucial in graphene synthesis for the development of graphene-based electronics. Numerous investigations have found that a reasonably designed binary alloy can effectively overcome the defects of pure metal and activate the self-limited growth of a monolayer of graphene. Graphene films were prepared on the Ni@Cu substrate by a chemical vapor deposition method. Ni@Cu is a novel Cu based substrate whose surface is alloyed with Ni atoms. In this paper, the advantages of graphene film synthesis on this new substrate were demonstrated through experiments, including the influence of the fast cooling process on the growth of graphene film, the influence of the proportion of Ni on the growth thickness of graphene film, and the transfer process of graphene film from this substrate.