AbstractMoS2 nanoparticles supported on gold nanoparticle films (AuNP/MoS2 films) were constructed by a simple two‐step drop‐casting modification process on a glassy carbon electrode. The films realized a direct four‐electron pathway for the oxygen reduction reaction (ORR) in alkaline media with an onset potential of −0.10 V versus the saturated calomel electrode. The films exhibited superior stability and better electrocatalytic performance than commercial Pt/C. Electrochemical studies and composition characterization illustrated that the enhanced catalytic activity of the AuNP/MoS2 films could be attributed to the synergistic effect of the positive onset potential of the gold nanoparticles for the ORR and the four‐electron oxygen reduction properties of the ultrasmall MoS2 nanoparticles, which is different from gold nanoparticle and MoS2 nanoparticle modified electrodes.