A FeCo catalyst obtained by thermolysis of double complex salts (DCSs) was used for the selective hydrogenation of CO<sub>2</sub> to CH<sub>4</sub>. The DCS-based catalyst did not require activation, and its structure remained unchanged either during high-temperature treatment with H<sub>2</sub> or CO or under the process conditions of CO<sub>2</sub> hydrogenation; therefore, the catalyst selectivity was not subject to structural changes.