AbstractA study of the phosphorescence emission from the commercial polyolefins, polyethylene, polypropylene and poly‐4‐methylpentene‐1 and the polyamides, nylon 6/6, 6, 11 and 12 is presented and the origin of the emission discussed. Impurity centres in the polymer are responsible for the emission, being present either as groups directly attached to the polymer backbone or as discrete molecules within the polymer matrix. These impurities can play an important part in the thermal and photochemical oxidation of the polymer. Therefore, changes in the phosphorescence spectra can provide valuable information on the mechanisms of both degradation proc