A novel 10%Co/MIL-53(Al) nanohybrid based on the microporous metal-organic framework MIL-53(Al) prepared by MW-assisted synthesis exhibits the properties of a bifunctional catalyst with activity in CO2 hydrogenation to CO and consecutive synthesis of liquid hydrocarbons from carbon monoxide formed. The observed increase in the CO2 conversion in comparison with the thermodynamically possible conversion is assumed to be due to the expected shift of the equilibrium toward the formation of CO as a result of its further rapid conversion to hydrocarbons by the Fisher-Tropsch reaction.