Organic-inorganic perylene diimide modified AgBr photocatalyst (PDISA/AgBr) was produced using a chemical co-precipitation method. The chemical structure, surface element composition, and appearance morphology of the prepared photocatalyst were characterized by XRD, FTIR, XPS, and SEM. The test results showed that the introduction of PDISA could broaden the light absorption range and enhance the light absorption ability of AgBr, meanwhile, promote the separation of photo-induced charge. Under light irradiation, PDISA/AgBr composite might effectively degrade Rhodamine B (RhB) organic pollutant. Compared with bare AgBr, the degradation rate of PDISA/AgBr was increased 4.21 times. The main active substance that played a role in the photocatalytic degradation process was ·O2−. Finally, based on the obtained results, the type Ⅱ mechanism is inferred.