Transition metals incorporated into molybdenum sulfide and tungsten sulfide matrixes are promising candidates for hydrogen evolution due to the unique chemical and physical properties. Here, we first describe a general strategy for the synthesis of rod-like ternary refractory metal sulfides (MWSx; M=Ni, Co, Fe and Mn) through a simple hot-injection method. The newly developed materials are affirmed as valuable alternatives to noble metal Pt due to their simple fabrication, inexpensive and impressive catalytic performance. We present that highly efficient catalysts for the hydrogen evolution at a polarized water/1,2-dichloroethane (DCE) interface by using the decamethylferrocene (DMFc). Kinetics of hydrogen evolution studies are monitored by two phase reactions using UV/Vis spectroscopy, and also further proved by gas chromatography. These ternary refractory metal sulfide catalysts show high catalytic activities on hydrogen evolution comparable to platinum. The rate of hydrogen evolution for the MWSx catalysts changed in the order Ni>Co>Fe>Mn according to the type of first row transition metals.