The refractive index of thin copolymer film was controlled by photo-degradation of chromophores in the copolymer. FTIR and UV/Vis spectroscopy were employed to elucidate the effect of chemical structure on refractive index changes after photobleaching. The decrease of refractive index of the film by photobleaching can be ascribed to the decrease of polarizability of polymer molecules through breakage of C =C bond in the chromophore. Due to the selective photoreaction of the chromophores which align along the film plane, refractive index of the copolymer film measured in TE mode decreases faster than that in TM mode. Polarized ATR-FTIR spectroscopy was used to verify such a difference in refractive index of the film.