Hydrogen evolution reaction (HER) is kinetically slow as a necessary half-reaction in water-splitting. It requires high-efficiency electrocatalysts to reduce the overpotential and improve energy conversion efficiency. Transition-metal electrode materials with high stability and efficiency have become the frontiers of energy conversion and storage fields. The present work involves the investigation of transition metals as electrocatalysts for HER. On the other hand, various carbon nanomaterials, including carbon nanotubes, activated carbon, and graphene for high-performance electrocatalysts, have been successfully shown. Still, their performances must be improved (using phosphorus-doped graphene) for wider and more challenging applications. The Ni-Co-V@PrGO was synthesized through a simple method with an amorphous structure that enhanced catalytic activity toward hydrogen evolution reaction with a Tafel slope of 80 and 58 mV dec−1 (counter electrode: Pt) and 85 and 118 mV dec−1 (counter electrode: graphite) in alkaline and acidic media, respectively. Hereupon this research presents a simple and efficient high-performance electrocatalyst for HER.