The shape-controlled synthesis of nanostructured materials has opened up new possibilities toimprove their physical and chemical properties. In this work, new types of monoclinic structuredBiVO4 with complex morphologies, namely flowerlike, disclike, tubelike and platelike shapes, have beensynthesized in a binary green solvent (water and ethanol) through controlling reaction conditionssuch as solvent, pH value, concentration of precursors and reaction temperature. The morphology ofBiVO4 can transform from three-dimensional (3D) flowerlike superstructures andhexagonal-prismatic nanotubes to two-dimensional (2D) platelike and disclikestructures. UV–vis absorption spectra show that all of the prepared nano- andmicrostructures can respond to visible light and the optical properties ofBiVO4 samples are relevant to their structures. More importantly, the photocatalytic activities of variousBiVO4 samples are strongly dependent on their morphology for the degradation ofrhodamine B (RhB) under visible-light irradiation. The 2D (disclike and platelike)BiVO4 demonstrates better photocatalytic activity than 3D and bulkBiVO4. Among the nano- and microstructures, the nanoplateBiVO4 exhibit the highest photocatalytic activity for degradation of organicpollutants. Additionally, it is found that the different microstructure ofBiVO4 leads to the different degradation route for organic compounds of RhB.The reasons for the differences in the photocatalytic behavior for theseBiVO4 nanostructures are further discussed. The relationship between the microstructure and the photocatalyticactivity for BiVO4 may give clues for the preparation of photocatalysts with high activitybased on material morphology design. Moreover, the prepared 2DBiVO4 can be a good photocatalyst used in environmental pollution control.