In this work, Pt nanoflowers deposited on highly ordered TiO2 nanotube arrays (TNTs) by modification of reduced graphene oxide (RGO) nanostructures have been synthesized. The ternary complex (Pt-TNTs/RGO) displays efficient electrocatalytic performance toward methanol oxidation in alkaline medium. The electrochemical impedance spectroscopy (EIS) and responsive photocurrent results indicate that the presence of graphene could effectively promote charge separation during electrocatalytic process. Interestingly, with assistance of visible light illumination, the electrocatalytic activity and stability of the ternary complex electrode toward methanol oxidation are distinctly improved. Both electro- and photo-catalytic processes for methanol oxidation contribute to the enhanced catalytic performance and stability. Moreover, the ternary electrode also displays efficient photoelectrocatalytic degradation of methylene blue (MB) under visible light illumination. The present work sheds light on developing highly efficient and long-term stability catalysts for methanol oxidation with assistance of visible-light illumination.