The aim of this study was to prepare a novel pH-sensitive smart film based on the addition of purple garlic peel extract (PGE) and TiO2 nanoparticles in a sodium alginate (SA)/polyvinyl alcohol (PVA) matrix to monitor the freshness of beef. FT-IR spectroscopy revealed the formation of stronger interaction forces between PVA/SA, PGE, and TiO2 nanoparticles, which showed good compatibility. In addition, the addition of PGE improved the tensile strength and elongation at break of the composite film, especially in different pH environments, and the color response was obvious. The addition of 1% TiO2 nanoparticles significantly improved the mechanical properties of the film, as well as the light barrier properties of the film. PGE could effectively be uniformly dispersed into the composite film, but it also had a certain slow-release effect on the release of PGE. PGE had high sensitivity under different pH conditions with rich color changes, and the color showed a clear color change from red to yellow-green when the pH increased from 1 to 14. The same change was observed when it was added to the film. In particular, by applying this film to the process of beef preservation, we judged the freshness of beef by monitoring the changes in the TVB-N value and pH value during the storage process of beef and found that the film showed obvious color changes during the storage process of beef, from blue (indicating freshness) to red (indicating non-freshness), and finally to yellow-green (indicating deterioration), which indicated that the color change of the film and the freshness of the beef maintained a highly consistent.