This invention discloses three-dimenional (3D) porous NiSe2 foam-based hybrid catalysts as highly efficient electrocatalystsfor hydrogen evolution reaction (HER) in water splitting. Porous NiSe2 foam was synthesized by direct selenization of commercial Ni foam. Then transition metal dichalcogenides (TMDC) such as CoS2, CoSe2, FeS2 or layered TMDC catalysts (MoS2, WS2, MoSe2, etc.) were grown on its surface. Due to the three-dimensional nature, good electrical conductivity, and mesoporous structures, 3D porous NiSe2 foam is a promising conductive scaffold to support the HER-active catalysts. The resulting hybrid catalysts exhibit outstanding catalytic performance in the HER, demonstrating low onset potential, large cathode current density, small Tafel slopes and large exchange current density. Most of the catalysts outperform the state-of-the-art catalysts and is closer to the performance of Pt catalysts. Considering the low cost and earth abundance of these compounds, they are promising alternatives to Pt currently used in water splitting. In particular, the starting material Ni foam is commercially available and in large scale, so the as-obtained hybrid catalysts can be used as sizable hydrogen evolving electrodes.