Abstract: Cesium tungsten oxide (Cs_xWO₃), as a non-stoichiometric functional material, has emerged as a research focus for energy-saving window coatings due to its near-infrared shielding properties arising from strong localized surface plasmon resonance (LSPR) effects. Traditional energy-saving window materials struggle to balance visible light transmittance with thermal insulation, often exhibiting light-induced discoloration and poor durability under UV exposure, thereby limiting their application. This study developed a CeO₂-Ce(OH)₃-Cs_xWO₃ composite coating to address photo-fading and UV aging issues. This coating maintains high visible light transmittance and near-infrared shielding capability while imparting excellent UV absorption and photocatalytic self-cleaning properties. Experiments demonstrate that when Cs_xWO₃ and CeO₂-Ce(OH)₃ are composite-coated at a 3∶1 mass ratio, the material exhibits over 74% visible light transmittance while achieving 94% near-infrared blocking efficiency, showcasing excellent spectral selectivity. In simulated heating tests at 28°C, the natural cooling rate reached 87%, confirming its effective solar heat radiation blocking capability. After 240 hours of simulated UV aging, the visible light transmittance decreased by less than 3%. Within 2 hours, the photocatalytic degradation rate of organic dyes reached 79%, demonstrating significant energy-saving benefits and promising long-term stability. Energy-saving windows constructed with this material offer superior photothermal regulation capabilities and anti-aging performance under UV exposure while ensuring ample indoor daylighting. This establishes a solid foundation for applications in intelligent thermal management of building envelopes.