Urchin-like Mo2S3 crystals, prepared via a molten salt assisted solid-state method, have been explored as novel electro-catalysts for hydrogen evolution reactions for the first time. Because of their unique three-dimensional structure and superior electrical conductivity, Mo2S3 exhibits better catalytic activity and stability in acidic media compared with the well-known two-dimensional 2H-MoS2 and 1T'-MoS2.