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Biological elastomer i.e., medium-chain-length poly-3-hydroxyalkanoate (mcl-PHA) and its graft copolymer were investigated for reactive coating application. They were composited with silver-doped zinc oxide (Ag-ZnO) to produce films with photocatalytic activities. The activities were assessed from the photodegradation efficiencies of methylene blue, Rhodamine B and Orange II dyes. The PHA composite films demonstrated sustained photocatalytic activities over repeated usage compared to neat PHA. The presence of Ag also inhibits microbial growth on the film surface. The composite film exhibited negligible toxicity effect when tested against Ceriodaphnia dubia. Potential and advantages of Ag-ZnO−PHA composite film in reactive coating applications are discussed.