In this study, trilayer films were prepared with an electrospun dextran interlayer, and gelatin outlayers fabricated by solvent casting and electrospinning, respectively. The trilayer film either with casted or electrospun outlayers showed an enhanced thermal stability, and acceptable color and opacity properties. Compared to the electrospun outlayers, the casted outlayers endowed the trilayer film with improved oxygen and water vapor barrier properties, and significantly enhanced the elastic modulus and tensile strength, indicating a greater resistance to deformation. The DPPH radical-scavenging activity assay indicated that the applied electrospun or casted outlayers effectively prolonged the release time of propyl gallate from the interlayer by 2-fold or more, with a sustained antioxidant activity. These results suggest the promising applications of multilayer films as active packaging materials with prolonged release of antioxidants to retard oil oxidation in the food industry.