So far, optical and effective radiative properties of polymer matrix based composites were investigated at temperatures well below their degradation temperature. At the same time, polymers exhibit temperature dependent physical properties and may undergo structural changes as their temperature raises. In this work, we employ the "Temperature-Controlled Spectrophotometry", a new method enabling to identify simultaneously phase transitions, thermal degradation and radiative properties of semi-transparent composites over a large temperature range. The method consists of measuring simultaneously the normal-normal and the normal-hemispherical transmittances and reflectances of the sample subjected to a laser irradiation with tuneable wavelength while the temperature is rised from room temperature up to 450 °C by means of a CO2 laser. Physical changes of the sample are identified from the temperature variation of normal-normal transmittance and specular reflectance measurements. Most of the results here are presented at a specific wavelength of 1070 nm but the proposed method is suitable over the semi-transparency spectral domain of the material by changing the wavelength of the probe laser. An inverse method for parameter identification based on normal-hemispherical measurements is employed to determine the transport effective radiative properties of the sample, namely the transport extinction coefficient and the transport scattering albedo from room temperature to 325 °C.