Herein, the synergistic effect of the silane coupling agent (KH550) and carboxymethyl chitosan (CMCS) co-modified boron nitride (BN) on the fireproof property of silicone acrylic emulsion-based composite is investigated to explore halogen-free coatings for flame-retarding plywood. Firstly, KH550 and CMCS co-modified BN improves its compatibility with the silicone acrylic emulsion.The results show that an appropriate loading of BN (2 wt%) enhances flame retardancy. The peak-heat release rate decreases from 86.01 to 54.95 kW m À2 , with the reduced fire growth index decreasing from 0.31 to 0.16 kW m À2 s À1 , and the average effective heat of combustion drops from 0.99 to 0.85 kW g À1 .Meanwhile, the x-ray diffraction results demonstrate that the co-modified BN reacts with the phosphoric acid generated by APP decomposition and transforms into BPO 4, enhances the thermal insulation of the coating. The pyrolysis kinetics confirms that the co-modified BN increases E α at 300-380 C by 23.4% and E α at 380-430 C by 21.5%. The water contact angle clarifies that the comodified BN significantly imparts higher water resistance to the coating. Generally, the high thermal conductivity of co-modified BN effectively achieves heat dissipation and facilitates the uniform charring of the composite coating, leading to the as-formed resilient residues for blocking flame development.