A novel pH-sensitive colorimetric film was prepared based on immobilizing red barberry anthocyanins (RBAs) within composite chitin nanofiber (CNF) and methylcellulose (MC) matrices. The incorporation of CNFs and RBAs improved their mechanical properties, moisture resistance, and UV–vis screening properties. Moreover, the RBAs could be used as colorimetric indicators to detect food spoilage because they are sensitive to changes in pH and ammonia gas production. The RBA-halochromic indicator changed from reddish/crimson → pink → yellow with increasing pH, and from pink → yellow with increasing ammonia vapor concentration. Furthermore, the smart films possessed good antioxidant and antimicrobial activity owing to the presence of the RBAs and CNFs. Finally, the validity of the indicator to monitor the freshness/spoilage of a model food (fish) was demonstrated. Overall, this study shows that active/smart films can be assembled from food grade ingredients that can protect and monitor the freshness of products, like meat and fish.