Photocatalytic reduction of CO to chemical fuels is attractive for solving both the greenhouse effect and the energy crisis, but the key challenge is to design and synthesize photocatalysts with remarkable performance under visible light irradiation. Efficient catalytic carbon dioxide reduction (CORR) with light is considered a promising sustainable and clean approach to solve environmental problems. Herein, we found a new photocatalyst ([Mn(en)][VBO(OH)]) (abbreviated as MnV) based on the modifiability of polyoxometalates, in which Mn acts as a modifying unit to efficiently reduce CO to CO and effectively inhibit the hydrogen precipitation reaction. This Mn modified polyoxometalate catalyst has a maximum CO generation rate of 4625.0 μmol g h and a maximum H generation rate of 499.6 μmol g h, with a selectivity of 90.3% for CO generation and 9.7% for H generation. This polyoxometalate photocatalyst can effectively reduce CO and inhibit the hydrogen precipitation reaction. It provides a new idea for the efficient photocatalytic carbon dioxide reduction (CORR) with polyoxometalate catalysts.