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Highly efficient photo-assisted electrocatalysis for methanol oxidation reaction (MOR) realizes the conversion of solar and chemical energy into electric energy simultaneously.Here we report a Pt-MXene-TiO2 composite for highly efficient MOR via a photoactive cascaded electro-catalytic process.With light (UV and visible light) irradiation,MXene-TiO2 serves as the photo active centre (photoinduced hole) to activate the methanol molecules,while Pt particles are the active centre for the following electro-catalytic oxidation of those activated methanol molecules.Pt-MXene-TiO2 catalyst exhibits a lower onset potential (0.33 V) and an impressive mass activity of 2,750.42 mA·mg-1Pt under light illumination.It represents the highest MOR activity ever reported for photo-assisted electrocatalysts.Pt-MXene-TiO2 also shows excellent CO tolerance ability and stability,in which,after long-term (5,000 s) reaction,still keeps a high mass activity of 1,269.81 mA·mg-1Pt (62.66% of its initial activity).The photo-electro-catalytic system proposed in this work offers novel opportunities for exploiting photo-assisted enhancement of highly efficient and stable catalysts for MOR.