With the development of social economy, environmental air quality has become a hot issue in the research field of indoor environmental comfort. TiO2 was an n-type semiconductor material with high chemical stability, strong corrosion resistance and non-toxic to human body. Using TiO2 photocatalysis performance to improve indoor air quality has become the research focus, but because TiO2 has high photocatalytic efficiency only under ultraviolet light source, and under visible light source the efficiency was low, which greatly limits the development of TiO2 in the field of indoor environment. Therefore, it is imperative to develop a TiO2 composite with good photocatalytic performance under visible light source. Using the method of element doping modification technology and improving the specific surface area can improve the photocatalytic reaction in the process of quantum efficiency and utilization of energy, in order to speed up the migration rate of electrons and holes to the surface and reduce the light composite probability of carrier. In this paper, with silicon dioxide SiO2 as template, polyvinylpyrrolidone as film-former, cerium nitrate Ce(NO3)3·6H2O and copper nitrate Cu(NO3)2·3H2O as modifier by sol-gel method to make Ce-Cu/TiO2 hollow microspheres with uniform particle size distribution, and its preparation process is divided into four stages, such as preparation stage of nano SiO2 ball template, preparation stage of Ce-Cu/TiO2-SiO2 composite microsphere gel, preparation stage of Ce-Cu/TiO2-SiO2 composite microsphere and preparation stage of Ce-Cu/TiO2 hollow microspheres. First, the products in each stage of Ce-Cu/TiO2 hollow microspheres were tested and analyzed by fourier transform infrared spectrometer (FTIR) and X-ray diffractometer (XRD), such as construction process of nano-SiO2 ball template was studied from a microscopic point of view in preparation stage of nano SiO2 ball template, attachment of TiO2 to nano-SiO2 ball template was studied in preparation stage of Ce-Cu/TiO2-SiO2 composite microsphere gel, effect of calcining process on crystal phase and structure of Ce-Cu/TiO2-SiO2 composite microsphere was studied in Ce-Cu/TiO2-SiO2 composite microsphere and effect of sodium hydroxide solution on the washing effect of nano-SiO2 ball template in Ce-Cu/TiO2-SiO2 composite microsphere in Ce-Cu/TiO2 hollow microspheres. Secondly, photoresponse performance of Ce-Cu/TiO2 hollow microspheres were tested and analyzed by ultraviolet-visible spectrophotometer (UV-Vis), in order to study the utilization efficiency of Ce-Cu/TiO2 hollow microspheres to visible light source. Finally, particle size distribution and microstructure of Ce-Cu/TiO2 hollow microspheres were tested and analyzed in order to uniform particle size distribution of Ce-Cu/TiO2 hollow microspheres. The results show that: the construction of amorphous nano-SiO2 ball template with amorphous structure using Si—O—Si group is conducive to the adhesion of polyvinylpyrrolidone on the surface of nano-SiO2 ball template, so as to control the cavity structure of Ce-Cu/TiO2 hollow microspheres. Ce-Cu doping basically enters TiO2 crystal, and rarely enters nano-SiO2 ball template crystal, thus inhibiting the transformation of TiO2 from anatase phase to rutile phase in Ce-Cu/TiO2-SiO2 composite microsphere. Ce-Cu-doped TiO2 can promote the formation of new energy levels within TiO2 and realize the capture of e- and h+ by photons with less energy, thus improving the utilization efficiency of Ce-Cu/TiO2 hollow microspheres to visible light source. The surface of Ce-Cu/TiO2 hollow microspheres is smooth and there is no obvious defect. Its morphology is good and the particle size distribution is even, that is, d90 is 219.54 nm, d50 is 151.60 nm, d10 is 103.84 nm, and d90-d10 is 115.7 nm. The above study provides a theoretical basis and research foundation for further obtaining uniform size distribution Ce-Cu/TiO2 hollow microspheres with good photocatalytic performance under visible light sources.