To obtain more sustainable and active food packaging materials, PHBV films containing 5% wt. of phenolic compounds with different molecular structures (ferulic acid, vanillin, and catechin) and proved antioxidant and antimicrobial properties were obtained by melt blending and compression molding. These were characterized by their structural, mechanical, barrier, and optical properties, as well as the polymer crystallization, thermal stability, and component migration in different food simulants. Phenolic compounds were homogenously integrated within the polymer matrix, affecting the film properties differently. Ferulic acid, and mainly catechin, had an anti-plasticizing effect (increasing the polymer glass transition temperature), decreasing the film extensibility and the resistance to breaking, with slight changes in the elastic modulus. In contrast, vanillin provoked a plasticizing effect, decreasing the elastic modulus without notable changes in the film extensibility while increasing the water vapor permeability. All phenolic compounds, mainly catechin, improved the oxygen barrier capacity of PHBV films and interfered with the polymer crystallization, reducing the melting point and crystallinity degree. The thermal stability of the material was little affected by the incorporation of phenols. The migration of passive components of the different PHBV films was lower than the overall migration limit in every simulant. Phenolic compounds were released to a different extent depending on their thermo-sensitivity, which affected their final content in the film, their bonding forces in the polymer matrix, and the simulant polarity. Their effective release in real foods will determine their active action for food preservation. Catechin was the best preserved, while ferulic acid was the most released.