Photocatalytic activity of TiO2 is known to be enhanced by surface fluorination due to the enhanced production of free center dot OH radicals in solution. Recently, hollow TiO2 microspheres with enhanced photocatalytic activity was developed through fluoride-mediated self-transformation, in which the high photocatalytic activity in degradation of acetone was attributed to the fluoride-induced enhanced crystallization of TiO2 without taking into account the effect of surface fluorination. This paper aims to re-evaluate the effects of fluoride-induced crystallization and surface fluorination on the photocatalytic activity of hollow TiO2 microspheres prepared by fluoride-induced self-transformation. Degradation of Brilliant Red X3B (X3B), an organic dye, was performed under different conditions to evaluate photocatalytic activity.