Designing effective, robust, and low-cost catalysts for oxygen evolution reaction (OER) is an urgent requirement yet challenging task in water electrolysis. In this study, a NiCoP-nanocubes-decorated CoSe2 nanowires arrays three-dimensional/two-dimensional (3D/2D) electrocatalyst (NiCoP-CoSe2-2) was developed for catalyzing OER via a combined selenylation, co-precipitation, and phosphorization method. The as-obtained NiCoP-CoSe2-2 3D/2D electrocatalyst exhibits a low overpotential of 202 mV at 10 mA cm-2 with a small Tafel slope of 55.6 mV dec-1, which is superior to most of reported CoSe2 and NiCoP-based heterogeneous electrocatalysts. Experimental analyses and density functional theory (DFT) calculations proof that the interfacial coupling and synergy between CoSe2 nanowires and NiCoP nanocubes are not only beneficial to strengthen the charge transfer ability and accelerate reaction kinetics, but also facilitate the optimization of interfacial electronic structure, thereby enhancing the OER property of NiCoP-CoSe2-2. This study offers insights for the investigation and construction of transition metal phosphide/selenide heterogeneous electrocatalyst toward OER in alkaline media and broadens the prospect of industrial applications in energy storage and conversion fields.