Experiments were carried out to investigate the influence of TiO2 surface fluorination on the photodegradation of a representative organic cationic compound, Methylene Blue (MB). The electropositive MB shows poor adsorption on TiO2 surface; its degradation performs a HO· radical-mediated mechanism. In the F-modified system, the kinetic reaction rate enlarged more than 2.5 fold that was attributed mainly to the accumulating adsorption of MB and the increased photogenerated hole available on the F-modified TiO2 surface.