Carbon/TiO2 composites were prepared via the reaction under Autogenic Pressure at Elevated Temperature (RAPET) using alkoxides as precursor, and then porous TiO2 hollow spheres were derived after removing the carbon ingredient by calcination at 600°C. The influence of surfactant additives, including the addition ratio and the nature of the surfactants, on the morphology and the structures of the Carbon/TiO2 composites and the derived TiO2 were also studied with scanning electron microscopy (SEM), X-ray diffraction (XRD), UV-Vis diffuse reflectance spectrophotoscopy (DRS) and nitrogen adsorption-desorption measurements. The results revealed that the morphology of the products turned to spherical and then fusiform and the structures turned from hollow to solid with the increasing of surfactant additive. The BET surface area of the hollow TiO2 was modified from 12m2/g to 57m2/g after calcinations. The XRD investigation indicates that the phases of the TiO2 in both the carbon/TiO2 composites and the derived TiO2 hollow spheres are anatase.