We demonstrate the high sensitivity of positron annihilation to compositional changes related to the thermal degradation of polyethylene (PE). Positron annihilation γ-ray and lifetime measurements were conducted for PE films with and without antioxidant (1000-ppm Ciba® IRGANOX® 1076), subjected to heat treatment at 100 °C for different periods, to a maximum of 30 days. For the film without antioxidant, the positron Doppler parameter (S) and ortho-positronium formation probability (Io−Ps) appreciably decreased with increased heat treatment times, whereas they barely changed for the film with antioxidant. This, together with the Fourier transform infrared measurements, demonstrated that the variations of S and Io−Ps are caused by the thermal oxidation of PE. The S parameter was found to be sensitive to the early stage of degradation, where the carbonyl concentration is inferred to be lower than 100 ppm. The high sensitivity results from the large positron mobility in PE and from the high positron affinity of oxygen-containing polar groups. This work provides the basis for an application of positron annihilation to sensitive detection of the initial degradation of PE and other nonpolar polymers. © 2003 American Institute of Physics.