Abstract The direct production of liquid fuels from CO 2 hydrogenation has attracted enormous interest for its significant roles in mitigating CO 2 emissions and reducing dependence on petrochemicals. Here we report a highly efficient, stable and multifunctional Na–Fe 3 O 4 /HZSM-5 catalyst, which can directly convert CO 2 to gasoline-range (C 5 –C 11 ) hydrocarbons with selectivity up to 78% of all hydrocarbons while only 4% methane at a CO 2 conversion of 22% under industrial relevant conditions. It is achieved by a multifunctional catalyst providing three types of active sites (Fe 3 O 4 , Fe 5 C 2 and acid sites), which cooperatively catalyse a tandem reaction. More significantly, the appropriate proximity of three types of active sites plays a crucial role in the successive and synergetic catalytic conversion of CO 2 to gasoline. The multifunctional catalyst, exhibiting a remarkable stability for 1,000 h on stream, definitely has the potential to be a promising industrial catalyst for CO 2 utilization to liquid fuels.