To elucidate the effect of polyvinylidene fluoride (PVDF) content on the combustion performances of aluminum-based solid propellants, Al@PVDF composite powders with coating contents ranging from 2% to 14% were prepared via the solvent and non-solvent method. The thermal reactivity of Al@PVDF composite powders and the energy release and combustion performances of the corresponding solid propellants were analyzed using thermogravimetric-differential scanning calorimetry, constant volume combustion tests, and simultaneous ignition experiments. Results indicate that the PVDF coating significantly enhances the thermal reactivity of aluminum. At the 6% PVDF coating content, the aluminum powder achieves the maximum thermal weight gain and exothermic enthalpy value of 78.96 % and 16.14 kJ·g?1, respectively. As the PVDF content increases, the energy release of solid propellants exhibits a trend of initial increase, following by a decrease, subsequent re-increase, and final decline, and reaching the maximum heat release of 6026 J·g?1 and pressurization of 4.45 MPa at 10% coating content. The ignition delay time of aluminum-oxygen reaction decreases from 53 ms to 12 ms. The pressure exponent of burning rate underwent a three-stage evolution, declining from 0.43 to 0.36, and further to 0.26. Analysis of condensed combustion products (CCPs) reveals a stage-dependent mechanism of PVDF content on combustion performances: the low coating content (2%~4%) inhibits molten aluminum agglomeration via pyrolysis products; the medium content (6%~8%) accelerates particle fragmentation and ignition but induces secondary agglomeration; the high content (10%~14%) generates excessive pyrolysis products that promote secondary fragmentation of agglomerates in gas-phase region.