The modification of photocathodes based on copper(I) oxide (COPC) by coating with ZnO nanoparticles or graphene oxide (GO) with different compositions and morphologies is considered. To cover the catalyst surface with graphene oxide, a technique was proposed via freezing of a sprayed aqueous suspension of graphene oxide followed by sublimation drying under vacuum conditions. This method improves the uniformity of the GO layer in comparison with the traditional drop-casting method and, as a result, improves the photocatalytic properties of the COPC. The influence of the composition and morphology of graphene oxide on the photocatalytic activity and stability of COPC has been established. ZnO nanoparticles and GO particles in contact with copper(I) oxide increase the photocurrent density by the more efficient separation of light-generated charge carriers, providing higher photocathode stability required in photocatalytic water splitting.