The obtainment of new materials with distinct properties by mixing two or more polymers is a potential strategy in sustainable packaging research. In the present work, a blend of cellulose acetate (CA) and zein (60:40 wt/wt CA:zein) was manufactured by adding glycerol or tributyrin as plasticizers (30% wt/wt), and garlic essential oil (GEO), complexed (IC) or not with β-cyclodextrin (βCD), to produce active packaging. Blends plasticized with tributyrin exhibited a more homogeneous surface than those containing glycerol, which showed major defects. The blends underperformed compared with the CA films regarding mechanical properties and water vapor permeability. The presence of IC also impaired the films’ performance. However, the blends were more flexible than zein brittle films. The films added with GEO presented in vitro activity against Listeria innocua and Staphylococcus aureus. The IC addition into films, however, did not ensure antibacterial action, albeit that IC, when tested alone, showed activity against both bacteria. These findings suggest that the mixture of CA and plasticizers could increase the range of application of zein as a sustainable packaging component, while essential oils act as a natural bioactive to produce active packaging.