Spinel zinc cobalt oxide (ZnCo O ) 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 e 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 ZnCo O 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 ZnCo O , while not working for Co O . The activity of the best spin-state-engineered ZnCo O outperforms other typical Co-based oxides.