β‐Carotene may represent an excellent natural antioxidant, and nanoscale encapsulation may contribute to development of a new technique for addition of antioxidants in active packaging. The objective of this work was to develop active biodegradable films with addition of free β‐carotene or β‐carotene–loaded lipid‐core nanocapsules and to evaluate the interaction with the polymeric matrix. The addition of free β‐carotene led to a decrease in the mechanical properties of films, result of their hydrophobic character and less interaction with the matrix. β‐Carotene nanocapsules caused the increase of colour intensity of films, elongation at rupture, and less light transmission, with the gradual increase according to increase in concentration. Films with β‐carotene nanocapsules presented greater protection of sunflower oil, with lower formation of oxidation products. The lower stability of free antioxidant led to behavior similar to control film, with less oxidation protection. The addition of nanocapsules can provide better interaction with the structure, since the encapsulated carotenoid exhibits solubility in aqueous medium and present better distribution, without altering the rapid biodegradability and thermal stability of films. The results show that encapsulated bioactive compounds can be used as hydrophobic natural antioxidants and added in active biodegradable packages for maintaining food safety and extending the shelf life.