Abstract Electrochemical water splitting is a common way to produce hydrogen gas, but the sluggish kinetics of the oxygen evolution reaction (OER) significantly limits the overall energy conversion efficiency of water splitting. In this work, a highly active and stable, meso–macro hierarchical porous Ni 3 S 4 architecture, enriched in Ni 3+ is designed as an advanced electrocatalyst for OER. The obtained Ni 3 S 4 architectures exhibit a relatively low overpotential of 257 mV at 10 mA cm −2 and 300 mV at 50 mA cm −2 . Additionally, this Ni 3 S 4 catalyst has excellent long‐term stability (no degradation after 300 h at 50 mA cm −2 ). The outstanding OER performance is due to the high concentration of Ni 3+ and the meso–macro hierarchical porous structure. The presence of Ni 3+ enhances the chemisorption of OH − , which facilitates electron transfer to the surface during OER. The hierarchical porosity increases the number of exposed active sites, and facilitates mass transport. A water‐splitting electrolyzer using the prepared Ni 3 S 4 as the anode catalyst and Pt/C as the cathode catalyst achieves a low cell voltage of 1.51 V at 10 mA cm −2 . Therefore, this work provides a new strategy for the rational design of highly active OER electrocatalysts with high valence Ni 3+ and hierarchical porous architectures.