Abstract With the development of hydrogen‐energy economy, it is urgent for researchers to explore high effective non‐noble metal electrocatalysts for oxygen evolution reaction (OER). Nickel‐based selenides have good conductivity and easy to regulate, which make them to be a promising OER electrocatalysts. Hence, many researchers engineering the structure of Nickel‐based selenides to further improve the OER performance. In this paper, NixFe 1‐x Se 2 porous‐nano‐microspheres with different ratio were synthesized. Results confirm that Fe not only affects the number of active sites in NiSe 2 , but also affects the intrinsic activity by forming lattice defects. Besides, introduction of Fe can change the redox ability of Ni cation and Se anion, thus, reducing the average valence state of Ni cation in NiOOH. As a result, the current density of OER is improved remarkably. When the current density reaches 10 mA cm −2 , the overpotential is only 285 mV.