Here, we report a high-performance catalyst MoSx@HSSZ-39 for conversion of COx to C2–4 hydrocarbons, in which MoSx clusters for COx hydrogenation at the first to intermediate methanol and then the zeolitic acid sites surrounding for further conversion of methanol to hydrocarbons. For CO2 hydrogenation, C2–4 hydrocarbons of ∼90% selectivity in organic products at 32.7% of CO2 conversion and excellent stability of 1000 h on stream are obtained. For CO hydrogenation, 95% of C2–4 hydrocarbons, 83% of LPG or 74% of propane selectivities at > 22% CO conversion and stable more than 200 h on stream are obtained. The cooperation among the MoSx clusters and the zeolitic acid sites constitutes the catalyst of intimate bifunction, which is the key to the high catalytic performance for COx hydrogenation.