Abstract: This study utilized hollow glass microspheres (HGM) as the substrate and sequentially coated them 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 of 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 materials (HGM&TiO2&ZnO), respectively. When HGM@TiO2@ZnO was added to an acrylic resin matrix at 40 vol%, 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.