Both transient photolysis and steady-state photo-degradation experiments were performed to gain insight into the kinetics and mechanisms of degradation of p-nitroaniline (p-NA) in aqueous solutions. Monophotonic photo-ionization of p-NA was characterized by 266 nm Laser Flash Photolysis (LFP). The quantum yield of e(aq)(-) was calculated. Radical cations and neutral radicals of p-NA were identified, respectively. The LFP of p-NA with H(2)O(2) in aqueous solutions was investigated for the first time. For steady-state photo-degradation, degradation of p-NA was observed at diverse irradiation conditions under 254 nm UV light. Direct photo-degradation of p-NA by 254 nm UV light in aqueous solution was very difficult. Once H(2)O(2) was added into the experimental system, degradation of p-NA was enhanced remarkably. In the absence of O(2), degradation rate increased rapidly along with the irradiation time and reached 80% at 10 min. p-NA could be totally removed after 15 min in UV/H(2)O(2) process. In the presence of O(2) and H(2)O(2), degradation rate increased linearly along with the irradiation time and reached 80% at 7.5 min. p-NA could be totally removed after 10 min. The mechanisms behind the photo-degradation of p-NA were discussed.