Gaseous NO was photocatalytically reduced at room temperature by photo-assisted selective catalytic reduction (photo-SCR) with ammonia over TiO₂ in this study. NO reduction efficiency and N₂ selectivity were determined from gases composition at the outlet stream of photoreactor. Effect of operating conditions, e.g. light intensity and inlet concentrations of ammonia and oxygen, on the NO reduction efficiency and N₂ selectivity were discussed to determine the feasible operating condition for photocatalytic reduction of NO. Experimental results showed that selective catalytic reduction of NO with ammonia over TiO₂ in the presence of oxygen was a spontaneous reaction in dark. The photoirradiation on the TiO₂ surface caused remarkable photocatalytic reduction of NO to form N₂, NO₂, and N₂O under 254 nm UV illuminations, while almost 90% of N₂ selectivity was achieved in this study. The ammonia and oxygen molecules played the roles of reductant and oxidant for NO reduction and active sites regeneration, respectively. The reduction of NO was found to be increased with the increase of inlet ammonia and oxygen concentrations until specific concentrations because of the limited active sites on the surface of TiO₂. The kinetic model proposed in this study can be used to reasonably describe the reaction mechanism of photo-SCR.