In the present study, peel waste of pitaya (Hylocereus spp.) was used to develop a novel active and functional film. The film was developed with a combination of the white-fleshed pitaya peel pectin (WPPP) as a biopolymer and white-fleshed pitaya peel betacyanins (WPPB) as an active constituent, respectively. Furthermore, montmorillonite (MMT), a cheap and environmental-friendly silicate material, was introduced into film matrix as a filler to reduce the moisture sensitivity of the film. The effect of the incorporation of WPPB on the properties of WPPP/MMT films was investigated. The colorimetric response of WPPP/MMT/WPPB to pH and ammonia was examined, respectively. Moreover, WPPP/MMT/WPPB-2 was employed to monitor the freshness of shrimp. The color of the film changed from redness to reddish-brown, and further to brownness, echoing the shrimp turned from fresh to spoiled. Therefore, WPPP/MMT/WPPB-2 composite films showed promise for the applications in monitoring the freshness of shrimp.