The poor environmental stability of natural anthocyanin hinders its usefulness in various functional applications. The objectives of the present study were to enhance the environmental stability of anthocyanin extracted from Lycium ruthenicum by mixing it with montmorillonite to form an organic/inorganic hybrid pigment, and then to synthesize allochroic biodegradable composite films by incorporating the hybrid pigment into sodium alginate and test them for potential applications in food testing and packaging. The results of X-ray diffraction, Fourier-transform infrared spectroscopy, and use of the Brunauer–Emmett–Teller method and zeta potential demonstrated that anthocyanin was both adsorbed on the surface and intercalated into the interlayer of montmorillonite via host–guest interaction, and the hybrid pigments obtained allowed good, reversible, acid/base behavior after exposure to HCl and NH3 atmospheres. The composite films containing hybrid pigments had good mechanical properties due to the uniform dispersion of the pigments in a sodium alginate substrate and the formation of hydrogen bonds between them. Interestingly, the composite films also exhibited reversible acidichromism. The as-prepared hybrid pigments in composite films could, therefore, serve simultaneously as a reinforced material and as a smart coloring agent for a polymer substrate.