Poly (α-dodecyl γ-glutamate) (PAAG-12) was successfully synthesized from poly(γ-glutamic acid) (PGGA) according to Nuclear Magnetic Resonance (NMR) analyses. PAAG-12 films were prepared and enriched with 5% α-tocopherol, with the aim of using them as novel antioxidant active packaging for food applications. Thermogravimetric Analysis (TGA) characterization determined that α-tocopherol improved thermal stability of films, which is beneficial for industrial processing. Polylactic Acid (PLA) films prepared with the same amount of α-tocopherol were used to set a comparative frame and both types of films were applied to two different food models to assess their protective action against oxidation. Water, 50% ethanol (EtOH) and 95% EtOH were used as food simulants and HPLC analyses were performed to determine diffusion and partition coefficients in PLA and the novel polymer, the latter exhibiting slower release rates. Primary oxidation was measured with peroxide value, which revealed that PAAG-12 films with α-tocopherol protected oil-in-water (O/W) emulsions up to 29 days, complying with the Codex Alimentarius.