In order to explore the effects of structure on combustion performance of aluminum/polytetrafluoroethylene （Al/PTFE）-based reactive materials and improve combustion performance of fluorine-based thermite， additive manufacturing technology （3D printing） was utilized to prepare Al/PTFE-based reactive materials with solid， hollow， core-shell， and confined hollow structures， as well as Al/CuO-based and Al/Fe₂O₃-based reactive materials with confined hollow structures. The microstructure， thermal performance， combustion rate， and gas production performance were assessed by scanning electron microscope （SEM）， differential scanning calorimetry （DSC）， high speed camera， and constant volume combustion chamber. The results show that each sample exhibits intact structure and uniform components. Under the circumstance of same mass， the samples with core-shell and confined hollow structures display lower heat release than that of samples with solid and hollow structures. The burning rate of samples with hollow， core-shell， and confined hollow structures is 1.44， 1.32， and 2.62 times higher than that of samples with solid structure， respectively. Obvious improvement in gas production performance and pressurization rate appears for samples with hollow and confined hollow structures， especially for samples with confined hollow structure. The burning rate of Al/PTFE， Al/CuO， and Al/Fe₂O₃ materials with confined hollow structure is significantly higher than that of corresponding samples with solid structure， particularly for Al/Fe₂O₃ materials. The approach to regulate combustion performance of lines by preparing materials with hollow structure is expected to provide a novel idea for designing new high-performance weapons.