A kind of nano-TiO2 with main structure of anatase crystal was prepared and supported on attapulgite. All these materials were characterized by XRD and TEM. The catalytic performance of the materials were evaluated by the polyester reaction, and the result showed: the catalytic activity of nano-TiO2 is close to Sb2O3, however, the catalytic property is unstable, and the hue b of polyester is larger; after the nano-TiO2 was supported on attapulgite, the catalytic center presented ideal dispersion state, the catalyst property were also more stable, and the hue b of polyester were better (from 14.05 to 8.17). Besides, the physical and chemical properties of the polyester influenced by the TiO2-complex catalyst were discussed by DSC and TGA, the result showed that the crystallization temperature of polyester increased by using TiO2-complex catalyst, and the content of diethylene glycol and the thermal performance were closed to normal polyester.