In this work, titanium dioxide (TiO2) was modified with reduced graphene oxide (rGO), and then coated on filter paper to prepare the rGT/FP photoelectrode for the photoelectrocatalytic (PEC) decolorization of methylene blue (MB). The physicochemical properties of the rGT/FP photoelectrode were characterized using scanning electron microscopy (SEM), X-ray diffraction (XRD) analysis and UV-Vis diffuse reflectance spectroscopy (DRS). The decolorization results demonstrated that the photocatalytic (PC) and electrocatalytic (EC) efficiency of the photoelectrode could be significantly improved by the modification of rGO. The improvement of PC and EC efficiency might attribute to the existence of rGO, which could extend the light-harvesting efficiency, promote the photocurrent response value and suppress the charge recombination. Furthermore, the PEC decolorization of MB using the rGT/FP photoelectrode presented higher efficiency than the sum of PC and EC decolorization, indicating the synergistic effect between the photo and electrical energy.