Hollow glass microspheres（HGM） was utilized as the substrate and sequentially was coated with eggshell-like TiO₂ and needle-like nano-ZnO through a rotational coating process and a two-step heterogeneous precipitation method， constructing a high-reflectance， low-thermal-conductivity core-shell-shell material HGM@TiO2@ZnO. Research demonstrates that the obtained HGM@TiO₂@ZnO exhibits a hollow core structure that reduces heat transfer efficiency. The dual-shell structure， comprising high and low refractive index layers， induces multi-level reflection and scattering of light， while the cavity structures formed between the needle-like nano-ZnO further decrease the thermal conductivity of HGM@TiO₂@ZnO， achieving a dual synergistic effect of "reflection-thermal insulation". Results indicate that the HGM@TiO₂@ZnO material achieves an average solar reflectance up to 88.64% in the visible-near-infrared（380—2500 nm） range， representing improvements of 25.6%， 6.2%， and 10.0% compared to HGM， HGM@TiO₂， and physically blended material HGM&TiO₂&ZnO， respectively. When HGM@TiO₂@ZnO was added to an acrylic resin matrix at volume fraction of 40%， the resulting coating exhibited an average solar reflectance of 72.86% and a thermal conductivity as low as 0.08 W·m-1·K-1. Compared to coatings with the same volume fraction of HGM added to the acrylic resin， the reflectance increased by 5.4%， while the thermal conductivity decreased by 34%. Thus， this study elucidates the synergistic regulation mechanism of the core-shell-shell hierarchical structure on photothermal performance， providing theoretical support and material foundations for the development of high-efficiency thermal-reflective and insulating functional coatings.
