In this paper we investigate the optical properties of thin films produced through the layer-by-layer (LbL) technique with a poly (p-phenylene vinylene) (PPV) precursor and the Congo Red (CR) azodye. Some significant changes are observed when the PPV/CR film is irradiated with polarized laser. An increase of about 10 times in the PPV emission intensity was observed, with an irradiation time of 100min. Photoinduced birefringence measurements revealed that a high birefringence was produced in the region of the film submitted to photo-irradiation, while a photobleaching phenomenon was observed in the same region. However, such phenomena were not detected in measurements performed at low temperatures. The results indicate that a degradation process of the CR molecules is occurring with photo-irradiation, and the changes observed in the photoluminescence spectra are correlated with the combined effects of degradation and energy transfer between the PPV light-emitting conjugated segments and CR azochromophores.