In this study, a series of electrodes were prepared. The decrease of surface area compared with that of the pristine AC indicated the blocking of micropores on the surface of the activated carbons; was further supported by SEM, XRD, EDX. It was found that catalytic decomposition of methylene blue solution could be attributed to synthetic effects between the TiO2 photocatalysis and electro-assisted activated carbons network and that photoelectrocatalytic oxidation increased with added of Co and graphene composition.