AbstractThe exploration of non‐noble metal electrocatalysts with high catalytic activity and stability for oxygen evolution reaction (OER) has become particularly urgent. Here, FeNi‐based Prussian blue analogues (PBAs) were obtained by adding different solvents, where PBA particles preferentially grew on the surface plane/edge of coordination polymer precursor (Ni‐ABDC) with various polarities. This resulted in the formation of FeNi‐PBA‐plane/edge morphologies, respectively. Notably, on account of more exposed PBAs, FeNi nanoparticles were uniformly supported on the porous N‐doped carbon nanomaterials. Among them, the calcined FeNi‐NC‐800 underwent an interesting pre‐activation process and exhibited a low overpotential of 281 mV at 10 mA cm−2 and a small Tafel slope of 82 mV dec−1 in 1.0 m KOH. This bimetallic sample showed superior OER activity and stability in comparison with control materials, which could be attributed to its abundant FeNi nanoparticles, high nitrogen content, large specific surface area, and synergistic effects between Fe and Ni atoms. In addition, relevant theoretical calculation on the optimal catalyst, FeNi‐NC‐800, further demonstrated its efficient OER performance with effective Fe‐doping in the Ni‐based oxyhydroxides.