Chemical vapor deposition (CVD) is regarded as the most promising technique for the mass production of graphene. CVD synthesis under vacuum is the most employed process, because the slower kinetics give better control on the graphene quality, but the requirement for high-vacuum equipment heavily affects the overall energy cost. In this work, we explore the possibility of using electroformed Cu substrate as a catalyst for atmospheric-pressure graphene growth. Electrochemical processes can produce high purity, freestanding metallic films, avoiding the surface defects that characterize the rolled foils. It was found that the growth mode of graphene on the electroformed catalyst was related to the surface morphology, which, in turn, was affected by the preliminary treatment of the substrate material. Suitable conditions for growing single layer graphene were identified.