Preparation of active and durable low-cost catalysts towards oxygen evolution reaction (OER) is essential for alkaline water splitting. Herein, porous Raney-Ni supported NiFe-LDH (NiFe-LDH/Raney-Ni) electrocatalyst was developed to achieve efficient and robust OER performance. Raney-Ni modulates the NiFe-LDH electronic structure by interfacial interaction. In-situ infrared shows the enhanced OH adsorption behavior, and in-situ Raman suggests that Raney-Ni promotes the formation of active NiFeOOH species on NiFe-LDH/Raney-Ni. Theoretical calculations found that the Fe atoms in NiFe-LDH/Raney-Ni enhances the charge transfer to the NiOOH species, which facilitates the formation of O* intermediates accelerating the OER process. The NiFe-LDH/Raney-Ni catalyst exhibits a low OER overpotential of 219 mV at 10 mA cm−2 in 1 M KOH with excellent stability for 200 h at 200 mA cm−2. Excellent performance is also achieved in alkaline electrolyzer test. This work presents a facile approach for the design of affordable and efficient alkaline OER electrocatalysts.