Hexagonal boron nitride (h-BN) had attracted increasing research interest in the field of energetic materials due to its unique properties. To address the challenges of surface functionalization of h-BN, the Hexanitrohexaazaisowurtzitane (CL-20)@bio-modified h-BN energetic composites were successfully prepared by secondary polymerization of poly-dopamine (PDA), tannic acid (TA) and tea polyphenols (TP) as the intermediate layer. Comprehensive characterization confirmed the successful formation of the polymer interface while preserving the crystal integrity of CL-20. The resulting composites exhibited significantly enhanced thermal stability and a markedly reduced impact sensitivity compared to CL-20. The improvement was attributed to the buffering and isolating effects of the bio-modified h-BN, which effectively mitigates the transmission of external mechanical stimuli. This work demonstrated a green and effective polymer-based interfacial engineering strategy for developing high-performance and safer energetic composites.