A simple bilayer system consisting of TiO 2 and chitosan (CS) biopolymer has been fabricated and immobilized onto a glass plate. The deposition properties of TiO 2 powder were improved by adding epoxidized natural rubber (ENR 50 ) and phenol-formaldehyde resin (PF) in the coating formulation. SEM analysis indicated that the degraded ENR 50 acted as macro-pores forming agent to generate macro-pores within the surface of TiO 2 layer and was quantitatively determined by TGA and EDX analyses as well. The highly porous structure of immobilized TiO 2 layer allows better diffusion of pollutants, increases the light penetration and improves the optical property as indicated by photoluminescence spectroscopy (PLS) analysis. Consequently, the photocatalytic activity and mineralization rate of the immobilized bilayer TiO 2 /CS system becomes approximately twice as fast as an immobilized TiO 2 single layer system and as good as TiO 2 powder in a slurry system. Moreover, the adsorption effect was extremely negligible and the photodegradation of phenol was mainly due to the photocatalytic process.