Photocatalytic oxidation of crosslinked chitosan-epichlorohydrin (CS-ECH) film was successfully achieved via an immobilized TiO2/CS-ECH photocatalyst system on a glass plate. Oxidation process of CS-ECH film was carried out by irradiating the system with a 45-W fluorescent lamp for 10h in ultra-pure water. The results indicate the formation of carbonyl functional groups and partial elimination of amine groups in the molecular structure of the oxidized CS-ECH film. This oxidized CS-ECH film has different optical properties, ionic conductivity, degree of transparency, swelling index and chemical stability than the fresh CS-ECH film. In the environmental applications, the TiO2/oxidized-CS-ECH photocatalyst system can have photodegradation and faster mineralization rate of phenol than both fresh TiO2/CS-ECH and TiO2/oxidized-CS photocatalyst systems. This simple photocatalyst system, therefore can be considered as an environmental friendly method to oxidize synthetic biopolymer and to improve the photocatalytic efficiency of TiO2 to treat wastewater.