The ultraviolet (UV) irradiation of a titanium dioxide (TiO2) film surface gives rise to two simultaneous phenomena: photocatalysis and superhydrophilicity. Photocatalysis has been thoroughly studied, but the mechanism governing superhydrophilicity remains controversial. The authors’ investigations show the effects induced by UV irradiation on the water adsorption and desorption on the TiO2 surface. The observations prove that superhydrophilicity cannot be solely induced by the removal of organic contamination via photocatalysis, but is associated with water adsorption most probably due to the appearance of hydroxyl groups on surface defects.