Thermooxidation of LDPE films by CO2 laser radiation, 10.6 μm, was characterized by Fourier transform infrared spectroscopy with attenuated total reflectance (FTIR-ATR). The formation of carbonyl and hydroxyl functional groups onto LDPE films was dependent on the fluency of CO2 laser. IR absorption of vinyl groups and C-O bond present in alcohols showed a decrease and an increase, respectively, indicating that CO2 laser radiation causes simultaneous formation and accumulation of hydroperoxides in LDPE films; furthermore, crystallinity of LDPE films irradiated with CO2 tends to increase. So, CO2 laser radiation is able to oxidize the LDPE films, obtaining a PE with similar spectroscopic properties to that of PE-BIO by a physical process.