The search for highly active earth-abundant elements and nonexpensive catalysts for hydrogen evolution reaction is a vital and demanding task to minimize energy consumption. Transition metals incorporated into molybdenum sulfides are promising candidates for hydrogen evolution because of their unique chemical and physical properties. Here, we first describe a general strategy for the synthesis of particle-shaped molybdenum-based ternary refractory metal sulfides (MMoSx; M = Fe, Co, Ni, and Mn) through a simple hot-injection method. The newly developed materials are affirmed as valuable alternatives to noble-metal platinum because of their simple fabrication, inexpensiveness, and impressive catalytic performance. We present highly efficient catalysts for hydrogen evolution at a polarized water/1,2-dichloroethane interface by using decamethylferrocene (DMFc). The kinetics of hydrogen evolution studies are monitored by two-phase reactions using UV-vis spectroscopy and also further proven by gas chromotography. These ternary refractory metal sulfide catalysts show high catalytic activities upon hydrogen evolution comparable to platinum. The rate of hydrogen evolution for the MMoSx catalysts changed in the order Ni > Co > Fe > Mn according to the types of first-row transition metals.