A facile, multi-step method has been developed for the fabrication of three-dimensional (3D) RGO/Ag@Pt/TiO2/CF electrode, which is composed of dendritic Ag@Pt core shell catalyst, reduced graphene oxide (RGO), TiO2 spheres, and carbon fiber (CF). The Ag@Pt dendrite and TiO2 spheres supported on CF are coated with the gauze-like RGO sheets. After complexing with RGO, the light absorption of RGO/Ag@Pt/TiO2/CF is extended to longer wavelength region in comparison with pure TiO2. Moreover, the photo-electrocatalytic performance of RGO/Ag@Pt/TiO2/CF electrode toward methanol oxidation is thoroughly studied by evaluating these factors including electrochemical activity surface area, peak current density, the poisoning tolerance against COads and long-term stability. The results demonstrate that photo-electrocatalytic performance of RGO/Ag@Pt/TiO2/TiO2/CF electrode is enhanced under the UV irradiation in comparison with widely used Pt/C-JM electrode and its counterpart, Ag@Pt/TiO2/CF electrode.