A novel thermal energy storage (TES) composites system consisting of the microPCMs based on n-octadecane nucleus and SiO2/honeycomb-structure BN layer-by-layer shell as energy storage materials, and wood powder/Poly (butyleneadipate-co-terephthalate) (PBAT) as the matrix, was created with the goal of improving the heat transmission and photothermal responsiveness of building materials. The microPCMs were made via mini-emulsion interfacial polycondensation and electrostatic self-assembly to anchor BN on the surface of the SiO2 shell. The two kinds of microPCMs we designed had regular spherical morphology, BN was successfully anchored outside the SiO2 shell, showing a honeycomb structure and good heat storage performance (140.4 J/g and 140.6 J/g). The thermal energy storage wood plastic composites (TES WPCs) had considerable energy storage capacity and temperature regulation ability. The TES WPCs with the unique honeycomb structure of BN-MicroPCMs (BN-WPC) had better heat transfer performance and photothermal conversion efficiency (69.54%), and the thermal conductivity, specific heat capacity and energy storage efficiency of which were increased by 75.06%, 87.06% and 200% respectively. Meanwhile, the unique honeycomb structure strengthened the interfacial bond strength of TES WPCs and brought satisfactory mechanical strength, and the tensile strength, elongation at break, bending strength and bending modulus of BN-WPC are increased by 51.16%, 97.01%, 81.28% and 742.74%, respectively compared with the WPC added with S-MicroPCMs (S-WPC). These results indicated that this research by designing the BN honeycomb structure layer on the traditional microPCMs surface, obtained the rapid thermal response of high-performance TES WPCs in residential construction, thermal energy storage, solar energy collection system and thermal regulation has broad application prospects.