With Ti(OBu)4 as precursor, and HAC as complexing agent, pure and Fe-doped TiO2 gelatins were prepared by sol-gel method. During the process of gel formation, metal ions were dispersed into the porous TiO2 matrix. Then, powders of pure nano-TiO2 and Fe-doped nano-TiO2 were prepared by drying, grinding and calcining at different temperatures. The grain size and phase structure of pure and Fe-doped TiO2 after calcined at different temperatures, were studied by X-ray diffraction (XRD) and Beckman Coulter Sorption Analysis. The results showed that, the Fe3+-TiO2 had better photocatalytic activity in degradation rate of methyl orange under sunlight. The degradation rate was up to 93% as the system was placed under sunlight for 5 h. The optimum calcination temperature for the best catalytic activity was determined to be 500°C, and the mechanism was discussed.