The performance of a direct methanol fuel cell (DMFC) highly depends on the anode catalyst. However, it is a grand challenge to construct a potential electrocatalyst featuring high intrinsic activity, a large electrochemical surface area and outstanding photoelectrochemical function for the methanol oxidation reaction (MOR). Herein, g-C3N4 composited with nano-SiC (g-C3N4/SiC) was prepared by evenly mixing urea and SiC followed by annealing at 550°C for different times. X-ray diffraction, thermogravimetric analysis, x-ray photoelectron spectroscopy, and Brunauer-Emmett-Teller surface area tests showed that g-C3N4 and SiC are bonded together by chemical bonds. Ultraviolet-visible (UV-Vis) spectroscopy characterization showed that the UV-Vis absorption edge of the g-C3N4/SiC sample is much higher than that of g-C3N4 or SiC. In addition, it was observed that an appropriate thickness of the g-C3N4 coating on the SiC surface would increase the photogenerated charge separation efficiency. Therefore, the obtained Pt/g-C3N4/SiC-90 exhibits a higher photoelectrocatalytic current density and long-term stability in comparison with Pt/SiC and Pt/g-C3N4 under the same conditions. Such a catalyst with high photochemical catalytic performance is thus promising for assembly of high-performance DMFCs.