CuO/TiO2 is modified by anionic, nonionic and cationic surfactant respectively in the preparation process. XRD, BET, UV-Vis, FTIR, 3D fluorescence and SEM are used to characterize the structure and photocatalytic activity of catalysts, which shows that crystal and UV-visible absorption characteristics of photocatalysts do not change with surfactant modification. All photocatalysts contain anatase TiO2 and CuO crystal, and their UV-visible absorption edges reach 900 nm. Whilse different kinds of surfactant lead to different amount of organic groups in photocatalytic surface, oxygen vacancies and the particle size of photocatalysts. Photocatalyst modified by anionic surfactant has the highest photocatalytic activity, because it has the richest organic groups and oxygen vacancies, and its particle size is the smallest. In contrast, photocatalyst modified by cationic surfactant has the lowest photocatalytic activity. In addition, degradation of dibutyl phthalate photocatalyzed by sodium dodecyl sulfate modified photocatalysts reaches at 93%.