Direct synthesis of liquefied petroleum gas (LPG) from syngas was carried out over hybrid catalyst consisting of methanol synthesis catalyst and Y zeolite modified with Pd and Ca by different methods. The decrease of CO conversion was mostly attributable to the sintering of Cu in methanol synthesis catalyst. On the other hand, coke deposition on the Y zeolite was the main reason for the decrease of LPG selectivity. The introduction of Ca decreased the strong acid sites of Y zeolite, suppressed coke formation, and thus improved the stability of hybrid catalyst. Direct synthesis of liquefied petroleum gas (LPG) from syngas was carried out over hybrid catalyst consisting of methanol synthesis catalyst and zeolite modified with Pd and Ca by different methods. The decrease of CO conversion was mostly attributable to the sintering of Cu in methanol synthesis On the other hand, coke deposition on the Y zeolite was the main reason for the decrease of LPG selectivity. The introduction of Ca decreased the strong acid sites of Y zeolite, suppressed coke formation, and thus improved the stability of hybrid catalyst.