In order to obtain the metal alloy composite fuel with pressurization effect， Al/Mo/PMF composite powder was prepared by a combination of vacuum suspension smelting， ultra-high temperature gas atomization and mechanical alloying. The phase， morphology and thermal properties of the composite powder were analyzed by XRD， SEM， TG/DTA. The combustion enthalpy and pressurization properties of the composite powder was measured by oxygen bomb calorimeter and constant volume isothermic combustion experiments. Results show that PMF distributes homogeneously in the composite particles after mechanical ball milling， which is helpful to improve the thermal reactivity of the powder and advance the initial reaction temperature. The extra pressurization effect was obvious due to the production of AlF₃ and MoO₃ with low boiling point. The extra pressurization generated by the combustion of Al/Mo/PMF 64/16/20 composite powder was 4.49% higher than that of pure Al powder. With the increase of PMF in the composite， the combustion enthalpy and combustion completeness of the composite powder decreased. The measured combustion enthalpy of Al/Mo/PMF 76/19/5 composite powder was 22541.8 J∙g^-1， while the measured combustion enthalpy of Al/Mo/PMF 64/16/20 composite powder was 16788.5 J∙g^-1. When the PMF content was 5%， the composite can burn completely， meanwhile the extra pressurization can be presented effectively. The corresponding maximum pressure was 3.430 MPa. In addition， the oxidation process and the mechanism of Al/Mo/PMF 76/19/5 composite powder were also studied.