The chemiluminescence of UV irradiated aromatic-aliphatic polyesters (Ecoflex and PBAT) and polylactic acid (PLA) was examined in nitrogen and oxygen atmospheres during the non-isothermal temperature runs in the interval from 40 to 250 °C and isothermally from 150 to 190 °C. The non-isothermal thermogravimetry and FTIR spectroscopy have been used for the characterization of differences in original samples. The temperature maxima of peroxidic peaks in nitrogen scaling their stability were compared and found to be in the order PBAT < Ecoflex < PLA. Their positions on the temperature scale that correlate well with the melting temperature of the respective polymer have been discussed. With prolongation of the UV irradiation period, the intensity of peroxidic peaks increased. On the other hand, the effect of pre-irradiation on non-isothermal runs of chemiluminescence measured in oxygen was not as distinct as for measurements in nitrogen. The deconvolution of the non-isothermal chemiluminescence runs in nitrogen revealed two kinds of peroxides in irradiated samples.