Freshness indicating films containing anthocyanins are one type of smart packaging technology. Anthocyanins in the films can show visual color changes when food spoilage occurs, thereby indicating the freshness degree of food in real-time. Rhododendron simsii is a landscape plant with attractive flowers that are abundant in anthocyanins. In this study, smart packaging films were prepared by embedding 2% and 4% R. simsii flower anthocyanins (RA) in locust bean gum- (LBG) and polyvinyl alcohol- (PVA) based matrices. The micro-structure, barrier, mechanical, thermal, antioxidant, and color-changeable properties of the films were determined. The potential application of the films in indicating the freshness of shrimp at 4 °C was also investigated. Results showed that the RA interacted with the LBG/PVA matrices through hydrogen bonds, which significantly improved the barrier, mechanical, thermal, antioxidant, pH-sensitive, and ammonia-sensitive properties of the films. Meanwhile, the performance of the films was remarkably influenced by the content of the RA. The film containing 4% RA had the highest light blocking ability, tensile strength (38.32 MPa), elongation at break (58.18%), and antioxidant activity, and also showed the lowest water vapor permeability (22.10 × 10−11 g m−1 s−1 Pa−1) and oxygen permeability (0.36 cm3 mm m−2 day−1 atm−1). The films containing 2% and 4% RA could effectively change their colors when the level of total volatile basic nitrogen in the shrimp exceeded the safe value, which demonstrated the suitability of the films for indicating the freshness degree of shrimp.