Time - resolved pulse radiolysis and laser flash photolysis has been used to study the Photo—Fenton degradation of aniline. Using laser flash photolysis technique, it is demonstrated that aniline in aqueous solution is ionized by 308 nm photon to give hydrated electron and neutral radical resulting from rapid deprotonation of radical cation of aniline. The pKa value is found to be 7.5,and the quantum yield of the photo ionization is 0.08. Time ,-, resolved pulse radiolysis has been used to study the reaction of aniline with •OH,and it was established that 36% •OH radical react directly with the - NH,2, moiety resulting in anilino radical. The main primary process (54%) is the ortho — directed •OH — adduct. The remaining 10% •OH attack most probably the para position of the aniline ying.