This study investigated the potential use of oxidation in a photoelectrocatalytic cell for bleaching p-nitrosodimethylaniline. The Ti/TiO2 used as photo-anode was prepared by a pulsed laser deposition method. The TiO2 coatings were found to have rutile and anatase structures consisting of approximately 10 and 15 nm in diameter, respectively. A relatively high degradation rate of p-nitrosodimethylaniline was recorded using the photoelectrocatalytic cell, compared to those measured during conventional electrochemical oxidation, direct photolysis and photocatalysis processes. The influence of different parameters such as crystallographic structure of Ti/TiO2, type of cathode, potential applied, electrolysis time, UV irradiation and initial pH were investigated. The photoelectrocatalytic cell using Ti/TiO2 (anatase structure) as photo-anode and vitreous carbon as cathode operated at a current intensity of 0.1 A for 120 min with 254 nm of UV irradiation was found to have the best conditions to remove high amounts of p-nitrosodimethylaniline (22.6 x 10(-3) mM h(-1)).