B@PDA and B@PDA@AP core-shell structured composites were synthesized successfully via the solvent-antisolvent method. PDA, functioning as an effective binder, modifies the B surface and anchors AP onto it. Analysis of the stable combustion process of B@20%PDA@15%AP and B/15%AP showed that B@20%PDA@15%AP exhibited more intense and complete combustion, with larger flame morphology and faster flame propagation. PDA enhances mass and heat transfer between B and AP, accelerates reaction rates, and mitigates AP decomposition splash, sustaining better gaseous phase combustion. This research offers strategies for tailoring the energy release of the B/AP and advancing its application in energetic materials.