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In this paper, a new two-dimensional (2D)/2D composite of Bi2WO6/MoS2 was facile synthesized, and then was used as supporting material for depositing Pt nanoparticles. The as-synthesized Pt-Bi2WO6/MoS2 was extended into photo-assisted electrocatalytic oxidation of methanol, which is a model anode reaction for direct methanol fuel cell. Compare with traditional electrocatalytic process, Pt-Bi2WO6/MoS2 displays 1.5 times enhanced electrocatalytic performance on methanol oxidation with assistance of visible light irradiation and 2.2 times for commercial Pt/C. Besides, from the results of chronoamperometric and chronopotentiometry experiments, the stability of Pt-Bi2WO6/MoS2 electrode is clearly improved under visible light irradiation. The synergistic effects of photo-and electro-catalytic in the heterojunction of Pt-Bi2WO6/MoS2 in favor of the above enhancement. This research gives more insights in the fields of photo-assisted traditional electrocatalytic application by constructing of semiconductor heterojunction carrier.