Photocatalysis as a green and efficient pollutant degradation technology, displaying great potential in environmental purification. By one step hydrothermal method in this study, flower-like Bi2WO6 with a large specific surface area was obtained, and the preparation of biomass carbon modified Bi2WO6 with sorghum stalks was also proposed to construct a series (BWO/x%C). The composites were effectively characterized in terms of several aspects of structure and properties. With the dyes rhodamine B and diclofenac as typical organic pollutants, the photocatalytic activity of the proposed photocatalysts was evaluated. Under visible light irradiation, the removal of rhodamine B by BWO/4%C reached 97.27% within 50 min and that of diclofenac reached 96.19% within 120 min, which were significantly favorable to single-phase Bi2WO6. The superiority of this system BWO/4%C is mainly due to its large specific surface area (33.51 m2/g), which provides additional reaction sites for contaminants. The UV–Vis DRS findings indicated that the modified biomass C reduced the band gap of Bi2WO6 and improved the availability of Bi2WO6 to visible light, and the separation efficiency of the electron and hole pairs of Bi2WO6 was improved due to the strong electron transfer ability of biomass C. The analyzing results of free radical trapping experiments confirmed that h+ and •O2- are the main active substances involved in the photodegradation reaction. The results of five cycle experiments exhibited that the degradation rate of rhodamine B still reached higher than 90%, confirming the good stability of the prepared material. Finally, a feasible degradation mechanism was proposed for the degradation of rhodamine B and diclofenac. It offers new ideas for the development of composite nano-photocatalytic materials targeting difficult-to-degrade organic pollutants.