<p>This study evaluates the structural, functional, and antioxidant properties of α-tocopherol loaded chitosan and alginate films fabricated as composites and multilayer configurations for potential use in food packaging. Results demonstrated that multilayer films exhibited greater thickness, reduced light transmittance, and higher haze as compared to composite films, with these effects enhanced upon α-tocopherol incorporation. Multilayer films exhibited a substantially lower water vapor transmission rate (WVTR) than composite films. Mechanical testing showed that multilayer films exhibited slightly higher tensile strength than composite films but lower flexibility, while tocopherol addition exerted only minor effects on mechanical behaviour. SEM analysis confirmed dense, compact structures in composite films and distinct bilayer organization in multilayer films, with α-tocopherol incorporation resulting in moderate surface roughness. Antioxidant activity measured via DPPH radical scavenging assay, increased significantly with α-tocopherol incorporation, in multilayer when compared to composite films. Water contact angle analysis revealed improved water resistance in multilayer films (70.67–72.41°) compared to composites (38.11–42.89°), suggesting increased hydrophobicity due to layered architecture. These results demonstrate that multilayer films, offer superior barrier properties, mechanical strength, antioxidant functionality, and water resistance compared to single-layer composites, highlighting their potential as active, eco-friendly packaging solutions.</p>