Multifunctional food packaging films were developed based on polyvinyl alcohol (PVA), sodium carboxymethyl cellulose (CMC), tea polyphenol (TP) and black carrot anthocyanin (CA). Results of Zeta potential, scanning electron microscopy, Fourier transform infrared spectroscopy and X-ray diffraction showed that CA enhanced the stability of the particle dispersion system through hydrogen bonding and electrostatic interactions, promoted the compatibility between TP and PVA-CMC (PC) substrates, and enhanced the binding between the components of the films. Because of the interaction of TP and CA, PC-TP-CA films had better water resistance and water vapor barrier properties, thermal stability, antioxidant and antimicrobial properties. PC-CA and PC-TP-CA films exhibited excellent UV-blocking properties. They also showed distinct color responsiveness in the pH range of 2–13, significant sensitivity to ammonia vapor in a short period of time and excellent color stability over 20 days of storage under different conditions. When the film was applied to fish, it was found that PC-TP-CA film could extend the shelf life of fish by 1–2 days and successfully monitor the freshness of the fish in real-time. Considering all the physical and functional properties, the non-toxic and biodegradable PC-TP-CA film has excellent potential as a new multifunctional food packaging material in the future.