Adsorption experiments and density functional theory (DFT) simulations indicated that Cu(acac)2 is chemisorbed on the monoclinic sheelite (ms)‐BiVO4 surface to form an O2‐bridged binuclear complex (OBBC/BiVO4) like hemocyanin. Multi‐electron reduction of O2 is induced by the visible‐light irradiation of the OBBC/BiVO4 in the same manner as a blue Cu enzyme. The drastic enhancement of the O2 reduction renders ms‐BiVO4 to work as a good visible‐light photocatalyst without any sacrificial reagents. As a model reaction, we show that this biomimetic hybrid photocatalyst exhibits a high level of activity for the aerobic oxidation of amines to aldehydes in aqueous solution and imines in THF solution at 25 °C giving selectivities above 99 % under visible‐light irradiation.