Bimetallic Ni-Fe catalysts (Ni/Fe, 1 : 1, 1 : 3, and 3 : 1) are synthesized and explored for their catalytic activity in semihydrogenation of internal alkynes using H2 gas in water-ethanol solution. Our findings revealed that over the Ni1Fe3 catalyst a high diastereoselectivity for Z-alkenes with a high conversion for a wide range of internal alkynes can be achieved at moderate reaction temperature (40 °C). Notably, the selectivity for the Z-alkenes is enhanced in the presence of n-butyl amine as an additive. Deuterium labeling experiments evidenced that H2 gas becomes dissociated homolytically over the catalyst surface to hydrogenate alkynes to alkenes. Synthesized catalysts were successfully characterized by HR-TEM, SEM, XPS, EDS, P-XRD and H2-TPD.