Today, innovation in the food packaging field can be summed up in the concepts of active and intelligent packaging. These two concepts refer to systems capable of interacting and monitoring the storage conditions of packaged food products, allowing them to control their shelf-life and quality at any time to ensure safer products for consumers. Among the active packaging, antimicrobial and antioxidant films seem to be the most promising as they allow to extend the shelf-life by reducing the proliferation of unwanted microorganisms and allow to maintain the organoleptic and nutritional qualities of food. Furthermore, considering the serious environmental impact caused by the volumes of plastic waste, the scientific world has turned towards the use of natural and biodegradable materials. Hence, this work is aimed at developing bio-films using several green techniques including electrospinning and solvent casting of biodegradable polymers such as zein, a prolamin extracted from corn, and polycaprolactone (PCL), a biodegradable synthetic polymer. The polymeric matrices obtained were functionalized by adding natural active compounds such as vanillin, present in vanilla pods, characterized by antimicrobial activity and (-tocopherol, contained in olive oil with high antioxidant properties. The results obtained are reported in terms of morphological characterization, migration tests, which have shown how it is possible to obtain a total release of the active compounds in 24 h under accelerated release conditions, showing the potential of these materials to be used as active food packaging.