Active films were prepared from poly(vinyl alcohol) (PVA) blended with itaconic acid (Ia), and with chitosan (Ch), enriched with tomato processing by-products extract (TBE) in order to develop new bioactive formulations for food packaging. The effects of two biopolymers (Ch, Ia) and of the incorporated TBE—containing phenolic compounds and carotenoids—were studied regarding the physical and antimicrobial properties of films; in addition, their influence on the total phenolic content, viscosity, and flow behavior on the film-forming solutions was investigated. The results showed increased physical properties (diameter, thickness, density, weight) of the films containing the TBE versus their control. TBE and Ch conferred significant antimicrobial effects to PVA films toward all the tested microorganisms, whereas the best inhibition was registered against S. aureus and P. aeruginosa, with a minimum inhibitory concentration of <0.078 mg DW/mL. The Ia-PVA films also exhibited some antibacterial activity against P. aeruginosa (2.5 mg DW/mL). The total phenolic content of the film-forming solutions presented the highest values for the TBE and Ch-added PVA samples (0.208 mg gallic acid/100 mL film-forming solution). These results suggest that the PVA + Ch film containing TBE can be used for the development of intelligent and active food packaging materials.