By a combination of theoretical and experimental design, we probed the effect of a quasi-single electron on the surface plasmon resonance (SPR)-mediated catalytic activities of Ag nanoparticles. Specifically, we started by theoretically investigating how the E-field distribution around the surface of a Ag nanosphere was influenced by static electric field induced by one, two, or three extra fixed electrons embedded in graphene oxide (GO) next to the Ag nanosphere. We found that the presence of the extra electron(s) changed the E-field distributions and led to higher electric field intensities. Then, we experimentally observed that a quasi-single electron trapped at the interface between GO and Ag NPs in Ag NPs supported on graphene oxide (GO-Ag NPs) led to higher catalytic activities as compared to Ag and GO-Ag NPs without electrons trapped at the interface, representing the first observation of catalytic enhancement promoted by a quasi-single electron.