Polyvinyl alcohol (PVA) has been widely applied in industries for its low cost, nontoxicity, biodegradability, and renewable advantages. However, its unstable structure may not meet some strong physical and mechanical needs. In order to enhance the performances of the PVA film, cellulose nanocrystals (CNCs), tannic acid (TA), and chitosan (CS), working as a reinforcer, a crosslinker, and an antimicrobial agent, respectively, were introduced into the PVA matrix. The results indicated that CNCs, TA, and CS were evenly distributed and cohesively incorporated within the PVA matrix, which contributed to the good mechanical properties and thermal stabilities of biocomposite PVA films. Besides, the addition of TA remarkably improved the antiultraviolet and antioxidant capabilities of PVA films, although the light transmittance declined slightly. It was also observed that the pure PVA film and PVA reinforced with CNCs were incapable of protecting against bacteria, while the ones with CS had prominent antibacterial properties to Escherichia coli and Staphylococcus aureus. Overall, the resulting film presented a high potential utilization as a food packaging material for its outstanding physical and mechanical performances.