Chinese bayberry (Myrica rubra Sieb. et Zucc.) fruit is a functional food rich in anthocyanins. In this study, anthocyanin-rich bayberry extract (BBE) was added into cassava starch to develop food packaging films with antioxidant and pH-sensitive properties. Results showed the main anthocyanin in BBE was cyanidin-3-O-glucoside (95.6%). The addition of 1 wt% of BBE into the film matrix resulted in a dense and compact internal microstructure, which greatly improved the water vapor permeability and tensile strength of the film. However, the addition of 2, 3 and 4 wt% of BBE into film matrix produced heterogeneous inner microstructures due to the formation of agglomerated BBE. The intermolecular interactions between BBE and the starch film matrix were through hydrogen binding. As compared with the starch film, starch–BBE films exhibited higher thicknesses, tensile strength, UV-vis light barrier and antioxidant properties. Moreover, starch–BBE films presented significant color changes when exposed to hydrogen chloride and ammonia gases. The pH-sensitive starch–BBE films were able to monitor the freshness of pork. Our results suggested that starch–BBE films could be used as smart and active packaging materials in the food industry.