Exploration of low-cost and high efficiency oxygen evolution reaction (OER) electrocatalysts is very important for the large-scale industrial application of alkaline water splitting driven by electricity. The present promising cobalt-based catalysts still leave room to meet the activity requirement. Here, a composite catalyst of α-Co(OH)2/Ag was synthesized by a simple photochemical deposition route, which was designed to improve the electrocatalytic activity for OER. Moreover, a photoinduced surface plasmon on Ag particles was found to further enhance the catalytic performance under low power of laser irradiation. Loading of silver nanocrystals on α-Co(OH)2 nanosheets can decrease the overpotential towards OER for 10 mA cm−2 from 320 to 288 mV, this value can be further decreased of 45 mV under 1000 mW of laser irradiation with a wavelength of 532 nm. The derivation of the catalyst during the OER process was examined, which indicates the structural transformation from α-Co(OH)2 to CoOOH. The photoinduced surface plasmon modulates the electronic structure of cobalt sites, facilitates the formation of active cobalt species, and induces the enhancement of catalytic activity. These findings may give some hints for plasmon-induced electrocatalysis and the design of advanced electrocatalysts.