CO₂ hydrogenation is an attractive way to store and utilize carbon dioxide generated by industrial processes, as well as to produce valuable chemicals from renewable and abundant resources. Iron catalysts are commonly used for the hydrogenation of carbon oxides to hydrocarbons. Iron-molybdenum catalysts have found numerous applications in catalysis, but have been never evaluated in the CO₂ hydrogenation. In this work, the structural properties of iron-molybdenum catalysts without and with a promoting alkali metal (Li, Na, K, Rb, or Cs) were characterized using X-ray diffraction, hydrogen temperature-programmed reduction, CO₂ temperature-programmed desorption, in-situ ⁵⁷Fe Mossbauer spectroscopy and operando X-ray adsorption spectroscopy. Their catalytic performance was evaluated in the CO₂ hydrogenation. During the reaction conditions, the catalysts undergo the formation of an iron (II) molybdate structure, accompanied by a partial reduction of molybdenum and carbidization of iron. The rate of CO₂ conversion and product selectivity strongly depend on the promoting alkali metals, and electronegativity was identified as an important factor affecting the catalytic performance. Higher CO₂ conversion rates were observed with the promoters having higher electronegativity, while low electronegativity of alkali metals favors higher light olefin selectivity.