3D printing technology enhances the combustion characteristics of hybrid rocket fuels by enabling complex geometries. However, improvements in regression rates and energy properties of monotonous 3D printed fuels have been limited. This study explores the impact of poly (vinylidene fluoride) and polydopamine-coated aluminum particles on the thermal and combustion properties of 3D printed hybrid rocket fuels. Physical self-assembly and anti-solvent methods were employed for constructing composite μAl particles. Characterization using SEM, XRD, XPS, FTIR, and μCT revealed a core-shell structure and homogeneous elemental distribution. Thermal analysis showed that PVDF coatings significantly increased the heat of combustion for aluminum particles, with maximum enhancement observed in μAl@PDA@PVDF (denoted as μAl@PF) at 6.20 kJ/g. Subsequently, 3D printed fuels with varying pure and composite μAl particle contents were prepared using 3D printing. Combustion tests indicated higher regression rates for Al@PF/Resin composites compared to pure resin, positively correlating with particle content. The fluorocarbon-alumina reaction during the combustion stage intensified Al particle combustion, reducing residue size. A comprehensive model based on experiments provides insights into the combustion process of PDA and PVDF-coated droplets. This study advances the design of 3D-printed hybrid rocket fuels, offering strategies to improve regression rates and energy release, crucial for enhancing solid fuel performance for hybrid propulsion.