To obtain multifunctional composites which had temperature-humidity properties and photocatalytic degradation ability to harmful substances, Ce-La/TiO2 hollow microspheres were prepared with Sol-Gel method. Then taking the Ce-La/TiO2 hollow microspheres as the carrier materials, the phase change materials—decanoic acid-palmitic acid was filled in Ce-La/TiO2 hollow microspheres’ cavities with vacuum absorption method to prepare Ce-La/TiO2 composites which had photocatalytic-mositure-heat properties. The materials of the main step of Ce-La/TiO2 composites were characterized with FTIR to study the establishment of SiO2 template, the bridging role of surfactant polyvinylpyrrolidone (PVP), the effect of filled decanoic acid-palmitic acid into Ce- La/TiO2 hollow microspheres. The photoresponisve of Ce-La/TiO2 composites was characterized by UV-Vis to study the effect of Ce-La doping to the TiO2 hollow microspheres’ light response ability. Further more, the microstructure of Ce-La/TiO2 composites was characterized with SEM to clarify the Ce-La/TiO2 composites preparation mechanism. The results show that, alkali environment which is provided by ammonium hydroxide is good for condensation reaction of tetraethoxysilane (C8H20O4Si), accelerating generate Si—O—Si groups at 78000 cm-1 to build SiO2 skeleton form kernel as the template to support the TiO2 wall materials. Adding PVP can generate —C—N— groups at 1 03500 cm-1, which is benefit for TiO2 attached to the surface of SiO2. Calcinate Ce-La/TiO2 hollow microspheres at high temperature can effectively remove PVP to avoid impurity ions into the composite system. Ce-La dopping makes the Ce-La/TiO2 composites’ absorption edge red shift, which is beneficial in enhancing the photocatalytic degradation ability under visible light. It also enhances the hydroscopicity of Ce-La/TiO2 composites due to —OH groups at 1 63000 cm-1. Decanoic acid-palmitic acid is fully filled in Ce-La/TiO2 hollow microspheres’ cavities, there is not much change in characteristic absorption peak of each component so the fundamental characteristics of each component could remain unchanged.