A novel electrocatalyst containing amorphous FeSeO x and Mo doped NiSe 2 (denoted as FeSeO x /Mo-NiSe 2) was developed via pseudocrystalline replication method and selenization treatment, and heteroatom doping and amorphous and crystalline (a-c) interface enables attractive OER performances. [Display omitted] • A novel FeSeO x /Mo-NiSe 2 electrocatalyst was desinged for water oxidation. • The optimized FeSeO x /Mo-NiSe 2 exhibits a low overpotential of 205 mV at 10 mA cm−2 for OER in alkaline solution. • The excellent performance is attributed to amorphous and crystalline (a-c) interface engineering and heteroatom doping strategies. Exploring integrated regulation strategies to boosting electrocatalytic performance is essential to design more efficient and inexpensive OER catalysts. Herein, amorphous and crystalline (a-c) interface engineering and heteroatom doping are integrated to construct a novel electrocatalyst containing amorphous FeSeO x and crystalline Mo-doped NiSe 2 (denoted as FeSeO x /Mo-NiSe 2) via pseudocrystalline replication method and selenization treatment. The resultant FeSeO x /Mo-NiSe 2 electrocatalyst with 3D hierarchical nanoarchitectures of nanorod arrays covered by interlocking nanoblocks exposes more active sites and accelerated reaction kinetics. Furthermore, a-c interface engineering and heteroatom doping can synergistically enhance the intrinsic activity and charge transfer capability of NiSe 2 by decreasing the electron diffusion distance and flexibly modulating the electronic structure, which contributes to boost the oxygen evolution reaction (OER) performance. Consequently, the obtained FeSeO x /Mo-NiSe 2 achieves a low overpotential of 205 mV at 10 mA cm−2, which outperforms many other transitions metal selenides electrocatalysts. Density functional theory (DFT) calculations demonstrate that the formation of an internal electric field between FeSeO x and Mo-NiSe 2 accelerates charge transport and optimizes the adsorption/desorption of oxygen-containing intermediates, thereby accelerating the reaction kinetics and improving the OER performance. This work serves as a point of reference for designing innovative metal selenides based electrocatalysts combining a-c interface engineering and heteroatom doping. [ABSTRACT FROM AUTHOR]