As food packaging evolves, consumer interests are shifting from traditional to intelligent food packaging systems. Intelligent packaging includes active components that display changes in a visual or interactive form perceivable by consumers. This offers real-time monitoring of the quality and shelf life of the packaged food and enhances transparency. For example, pH-sensitive natural pigment-based films change color in response to variations in pH levels, enabling the film/labels to reflect alterations in the acidity or basicity of the food inside the package. Natural pigments like anthocyanins, curcumin, betalains, chlorophyll, and carotenoids have been comprehensively reported for developing biodegradable pH-sensitive films of starch, protein, chitosan, and cellulose. Natural pigments offer great compatibility with these biopolymers and improve the other performance parameters of the films. However, these films still lack the strength and versatility of petroleum-based synthetic plastic films. But these films can be used as an indicator and combined with primary packaging to monitor freshness, time-temperature, and leak for muscle foods, dairy products, fruits and vegetables, and bakery products. Therefore, this review provides a detailed overview of pH-sensitive pigments, their compatibility with natural polymers, their role in film performance in monitoring, and their food packaging applications.