Anthocyanin extracts from purple tomato (PTA) were incorporated with polyvinyl alcohol (PVA), resulting in a series of colorimetric PVA/PTA films with PTA concentrations of 0%, 1%, 3%, and 5% (based on PVA). The role of anthocyanin on color response, Fourier-transform infrared (FTIR), thickness, water content, mechanical properties, antioxidant activity, and water vapor permeability (WVP) through the films was examined. In addition, its application in smart packaging to assess the freshness of shrimp was studied. It was found that the tensile strength, contact angle and WVP of PVA/PTA films increases with the addition of more PTA, while the elongation at break and water content decreased. FTIR analysis showed that there are interactions between PTA and the PVA matrix. The addition of anthocyanins caused significant improvement in the antioxidant properties of PVA films. Furthermore, the total volatile alkaline nitrogen (TVB-N), total plate count (TPC), and pH value of shrimp were monitored after 4 days of refrigeration, and the color change of the indexes was recorded. The PVA/PTA films changed color from purple to yellow-green during the storage time of 0–4 days for shrimp. This suggests that the film could be used in smart packaging as a real-time freshness indicator for shrimp.