[en] We observed for the first time that irradiation of phthalimide in methanol in the presence of TiO₂ affords N-hydroxymethyl-3-hydroxyphthalimidine as the final product in good yield. The chemical yield of depends on the amount of water in methanol solvent. Maximum yield was achieved when was irradiated in methanol containing 3 Χ 10^-2 vol% of water. The primary photoreduction products, i. e., reductive dimer and C-hydroxymethyl-3-hydroxyphthalimidine, were converted into the N-hydroxymethyl derivative in quantitative yields by the TiO₂-mediated photo-reactions. In addition, C-hydroxyethyl-3-hydroxyphthalimidine and C-hydroxyisopropyl-3-hydroxyphthalimidine, produced in ethanol and i-propyl alcohol, respectively, were also converted into by the TiO₂-mediated photoreactions. Mechanistic study and synthetic application of this photo-reaction are under progress. Photochemical reactions of some nitrogen-containing compounds catalyzed by semiconductors such as titanium dioxide (TiO₂) in solution phase have been extensively investigated. It was reported that various type of compounds are produced depending on the structures of reactants