Abstract: Catalytic properties of GdFeO₃ and GdMnO₃ perovskite-type oxides in CO hydrogenation processes is conducted. Complex oxides Gd(Fe/Mn)O₃ are synthesized by the sol–gel technology and characterized by X-ray diffraction, temperature-programmed reduction, and scanning electron microscopy. It is found that the iron-containing catalyst has fairly high catalytic characteristics; therefore, it provides lower temperatures of carbon monoxide hydrogenation. The presence of manganese in the catalyst leads to an increase in light olefin selectivity compared with the sample containing iron at the B-site. It is assumed that gadolinium cations are responsible for dissociative chemisorption, while iron and manganese cations are responsible for the formation of atomic hydrogen. The two catalysts exhibit resistance to carbon deposition.