In this work, we report a strong enhancement of photoluminescence (PL) intensity in PPV cast films upon laser irradiation in air, which competes with other quenching process related with formation of carbonyl groups. This increase of PL is dependent on laser intensity and film thickness. We observed that PL intensity increases up to 300% without significant changes in peak positions. This effect was accompanied by a blue shift of the absorption spectra and by the incorporation of carbonyl groups detected by infrared measurements.