BiVO4/MnO2 composite catalyst-oxidizer are successfully prepared by one-step hydrothermal method, and its structure and properties were analyzed by XRD, FTIR, SEM, EDS and UV-vis DRS. The catalytic-oxidative activities of the samples were evaluated by the degradation of Rhodamine B(RhB). The results exhibited that the composite formed the porous structure, the crystal structure of BiVO4 in BiVO4/MnO2 composite did not change, and shows a leaf-like profile with flaky combination’smorphology. The band gap of BiVO4/MnO2 is smaller than that of BiVO4. When the mass ratio of BiVO4/MnO2 was 10%, the composite showed the highest photocatalytic-oxidative activity. The degradation rate of RhB reached 98.4% at 20 minutes as the pH of solution was 5, and it is much higher than that of pure BiVO4(13.1%). Due to the oxidizing properties of MnO2, BiVO4-MnO2 composites can be used as photocatalytic-oxidants.