The design of electrocatalysts for oxygen evolution reaction (OER) remains a limitation of industrial hydrogen production by electrolysis of water. Excellent and stable OER catalysts can be developed by activating lattice oxygen and changing the reaction path. Herein, S and FeOOH on the Co(OH)2 nanoneedle arrays are introduced to construct a heterostructure (S-FeOOH/Co(OH)2/NF) as a proof of concept. Theoretical calculations and experimental suggest that the Co-O-Fe motif formed at the heterogeneous interface with the introduction of FeOOH, inducing electron transfer from Co to Fe, enhancing Co─O covalency and reducing intramolecular charge transfer energy, thereby stimulating direct intramolecular lattice oxygen coupling. Doping of S in FeOOH further accelerates electron transfer, improves lattice oxygen activity, and prevents dissolution of FeOOH. Consequently, the overpotential of S-FeOOH/Co(OH)2/NF is only 199mV at 10mA cm-2, and coupled with the Pt/C electrode can be up to 1 A cm-2 under 1.79V and remain stable for over 120h in an anion exchange membrane water electrolyzer (AEMWE). This work proposes a strategy for the design of efficient and stable electrocatalysts for industrial water electrolysis and promotes the commercialization of AEMWE.