Abstract A fruitful paradigm in the development of low‐cost and efficient water splitting systems for hydrogen generation is to search the highly active non‐noble catalysts towards hydrogen evolution reaction (HER). Here, the electrocatalytic HER activity of nanostructured amorphous nickel boride (Ni−B) alloy has been investigated. Amorphous Ni−B has exhibited excellent catalytic efficiency and long‐term stability for HER over a broad pH range, which is actually comparable to the performance of Pt. This high catalytic activity is due to the amorphous structure and the moderate electron structure of Ni−B. The Ni−B catalyst is easily obtained via electroless plating technique and we could get a supported Ni−B catalyst on desired substrates. Given the low cost, abundance, corrosion resistance, high efficiency and ease of fabrication, amorphous Ni−B is among the best alternatives to noble metal hydrogen evolution catalysts for water splitting.