ZnO nanostructures were obtained by electrodeposition on Ni foam where graphene was previously grown by chemical vapor deposition (CVD). The resulting heterostructures were characterized by X-ray diffraction and SEM microscopy and their potential application as a catalyst for the photodegradation of methylene blue (MB) was evaluated. The incorporation of graphene to the Ni substrate increases the amount of deposited ZnO at low potentials in comparison to bare Ni. SEM images show homogeneous growth of ZnO on Ni/G but not on bare Ni foam. A percent removal of almost 60% of MB was achieved by the Ni/G/ZnO sample, which represents a double quantity than the other catalysts proved in this work. The synergistic effects of ZnO-graphene heterojunctions play a key role in achieving better adsorption and photocatalytic performance. The results demonstrate the ease of depositing ZnO on seedless graphene by electrodeposition. The use of the film as a photocatalyst delivers interesting and competitive removal percentages for a potentially scalable degradation process enhanced by a non-toxic compound such as graphene.