AbstractSpinel zinc cobalt oxide (ZnCo₂O₄) is not considered as a superior catalyst for the electrochemical oxygen evolution reaction (OER), which is the bottleneck reaction in water‐electrolysis. Herein, taking advantage of density functional theory (DFT) calculations, we find that the existence of low‐spin (LS) state cobalt cations hinders the OER activity of spinel zinc cobalt oxide, as the t_2g⁶e_g⁰ configuration gives rise to purely localized electronic structure and exhibits poor binding affinity to the key reaction intermediate. Increasing the spin state of cobalt cations in spinel ZnCo₂O₄ is found to propagate a spin channel to promote spin‐selected charge transport during OER and generate better active sites for intermediates adsorption. The experiments find increasing the calcination temperature a facile approach to engineer high‐spin (HS) state cobalt cations in ZnCo₂O₄, while not working for Co₃O₄. The activity of the best spin‐state‐engineered ZnCo₂O₄ outperforms other typical Co‐based oxides.