Hydrogen evolution reaction (HER) catalysts including transition metal chalcogenides have been recognized as a class of very promising non-expensive and earth-abundant catalysts. Tremendous investigations on the binary and ternary metal sulfides/selenides have demonstrated extraordinary chemical and physical properties such as good structural stability and adjustable chemical composition. The ternary amorphous refractory metal selenides (MWSex; M = Fe, Co, Ni, Mn) have been synthesized by the hot-injection method. The NiWSex, CoWSex, FeWSex and MnWSex nanostructures have been used as catalysts for the hydrogen evolution at the biphasic systems of water and 1,2-dichloroethane with similar to a biomembrane. The catalytic activity differences of ternary metal selenides have been compared with each other taking into account transition metals which are changed in the order of Fe ≈ Mn ≪ Co < Ni. The catalytic activities of the MWSex have not been changed when adding of Fe and Mn into the tungsten selenide nanostructure, which may be originated from amorphous structures of FeWSex and MnWSex. Ni and Co addition into the tungsten selenide have improved the electrocatalytic HER activity when compared with only WSex.