Plasmon enhancement in electrocatalysis was investigated on pure Au nanoparticles (AuNPs) and an AuNPs-reduced graphene oxide (AuNPs/rGO) hybrid. Upon localized surface plasmon resonance (LSPR) excitation, hot charge carriers (hot electrons and holes) generate on the AuNPs. In the experiments, hot holes were scavenged by glucose and hot electrons could be efficiently transferred to the external electric circuit under a potential bias, resulting in an observable current enhancement. Then, the hot electrons' transfer efficiency can be quantitatively compared by the increased current response.It was found that the current density increased more obviously on the AuNPs/rGO hybrid than on pure AuNPs upon light irradiation. Due to the excellent electron mobility of rGO and the perfect electron affinity capacity, the hot electrons generated on AuNPs are efficiently transferred to the closely contacted rGO, then flow into the external circuit, generating current. The present study highlights the role of rGO in improving the separation of hot charge carriers to promote photocatalytic reactions.[a] X.