Electrocatalytic water splitting to produce green hydrogen is one of the important ways to develop sustainable energy systems. Highly active, low-cost amorphous alloys composed of transition metals Ni and Mo are widely regarded as efficient catalysts for hydrogen production. The catalysts represented by nickel-molybdenum (NiMo)-based amorphous alloys are focused on, the synthesis methods of amorphous alloys and their applications in the field of catalysis are summarized, and the application of NiMo alloys, NiMo-based medium entropy alloys, and NiMo-based high-entropy alloys are described respectively in electrocatalytic hydrogen evolution reaction (HER). In a word, NiMo-based amorphous alloy catalysts exhibit excellent hydrogen evolution performance by solving key scientific and technical problems with a reasonable function-oriented design. Finally, five issues in terms of preparation technology, component regulation, nanoscale, electronic structure and catalytic mechanism are proposed. This gives a clue for the design, preparation, structure-activity relationship and catalytic mechanism of catalysts.