As a continuation of our previous work on the kinetics of photocatalytic reduction of NO by CO on titaniumdioxide, interaction of a Degussa P-25 TiO ₂ photocatalyst with NO, CO, and NO-CO mixtures at ambient temperature has been studied by FTIR and TPD. Only reversible weak adsorption of NO on surface Ti⁴⁺ ions is found to occur in the dark. UV-vis irradiation greatly enhances the NO adsorption on Ti⁴⁺ and yields N₂O, NO^-, NO₂^-, and NO ₃^-surface species. After irradiation of TiO₂ in a CO atmosphere, IR bands of surface CO₂^-and CO ₃^-species appear in addition to a continuous IR absorption tail towards lower wavenumbers due to free carriers in the reduced semiconductor. When TiO₂ is exposed to a equimolar NO-CO mixture, N₂O and CO₂^-are formed without irradiation supposedly by the reaction 2 NO + 2 CO + O₂^-→ 2 CO₂^-+ N₂O. Subsequent light irradiation is accompanied by the accumulation of NO^-and Ti₄ +...NO complexes. No TiO₂ reduction occurs in this case. FTIR spectra show that NO^-produced by the photoinduced adsorption of NO can be eliminated by the following reaction: NO^-+ CO →^hv CO₂^-+ (1/2) N₂. It is believed that this reaction is a key step in the nitrogen production by the photocatalytic process. The data obtained enable us to refine the earlier proposed reaction mechanism and to directly prove some of its key steps.