The thermal stabilizing efficiency of a range of phenolic antioxidants (Lowinox CA22, Lowinox WSP, Lowinox TBP6, Irganox 3114, Irganox 1330, and Cyanox 1790) was determined in polyethylene films with chemiluminescence and hydroperoxide analysis and compared with standard systems based on Irganox 1010 and 1076. Under both nitrogen and oxygen conditions, good correlations were obtained between the two methods, confirming the importance and role of the hydroperoxide functionality and its stability in the oxidative process. Chemiluminescence decay rates correlated well with the initial corresponding hydroperoxide contents, which were measures of the antioxidant efficiencies in the polymer. The antioxidant structure and volatility (melting points) were important parameters to consider in any such correlations and related very much to the methodology and conditions of analysis (i.e., the temperature and atmosphere). Some of the antioxidants themselves under nitrogen exhibited strong chemiluminescence, which appeared to be a legacy associated with their manufacturing history and the partial oxidation of their structures, which gave peroxide functionalities. This was more notable for the complex antioxidant structures. Under oxygen, higher levels of chemiluminescence were observed, and this was indicative of some level of oxidation associated with the antioxidant structures. With temperature-ramping experiments, the chemiluminescence emission was significant and only observed at temperatures close to the melting points of the additives and/or polymer. Mobility was clearly an essential feature of this reaction emission because chemiluminescence was well observed when the molten state was reached. Under normal practical conditions, such levels of chemiluminescence, because of employed stabilizers, do not contribute significantly to the chemiluminescence emissions of stabilized polymer materials.