The synthesis, structural characterization and properties of a new bioinspired phenolic polymer (polyCAME) produced by oxidative polymerization of caffeic acid methyl ester (CAME) with horseradish peroxidase (HRP)-H2O2 is reported as a new sustainable stabilizer toward polyethylene (PE) thermal and photo-oxidative degradation. PolyCAME exhibits high stability toward decarboxylation and oxidative degradation during the thermal processes associated with PE film preparation. Characterization of PE films by thermal methods, photo-oxidative treatments combined with chemiluminescence, and FTIR spectroscopy and mechanical tests indicate a significant effect of polyCAME on PE durability. Data from antioxidant capacity tests suggest that the protective effects of polyCAME are due to the potent scavenging activity on aggressive OH radicals, the efficient H-atom donor properties inducing free radical quenching, and the ferric ion reducing ability. PolyCAME is thus proposed as a novel easily accessible, eco-friendly, and biocompatible biomaterial for a sustainable approach to the stabilization of PE films in packaging and other applications.