In order to improve the performance of electrical equipment, it is urgent to develop new high performance contact materials for electric power system. A novel preparation method of graphene/copper composite contacts was presented in this paper. The Ni-Cu alloy transition layer was prepared on the surface of copper (mass fraction was 0.999) by plasma-assisted processing. On such a transition layer, the graphene surface film was prepared by a high-powered continuous-wave laser in situ, covering the surface of copper as an independent coating to resist the damage of contact material. The plasma-assisted processing and laser processing processes of graphene composite contact materials were explored. The results show that the graphene/copper-based contact materials have excellent electrical characteristics, the resistance is similar to red copper, hardness is 1.8 times that of red copper, friction coefficient is only 0.06. This work can provide a new solution and a new material system for electrical materials.