AbstractOrganic–inorganic composite photochromic coatings receive significant attention in energy utilization and conservation due to their easy application and rapid photoresponse. However, their high sensitivity to moisture limits practical applications. This study fabricates organic–inorganic composite functional coatings using a simple one‐pot method, producing materials with excellent photoresponsive, water resistance, and thermal insulation. Unmodified phosphotungstic acid serves as the inorganic photochromic filler, while methacrylate derivatives act as the polymer matrix, resulting in coatings with high initial transparency (over 85%). After 5 min of UV exposure, the samples shift to nearly non‐transmittable states in the visible range and maintain color depth through 14 coloring‐erasing cycles. Unlike polyvinylpyrrolidone substrates, which absorb moisture and soften quickly, this coating has a static water contact angle of up to 91.7°, showing excellent water resistance. Additionally, the composite material provides effective heat insulation in simulated chamber experiments, lowering the temperature by 15 °C compared to untreated chambers. In summary, this composite coating, with its excellent thermal insulation, rapid light responsiveness, stable cycling performance, and outstanding waterproof capabilities, proves highly suitable for applications such as smart windows, information storage, and building energy efficiency.