Bismuth vanadate (BiVO4) microstructures with dumbbell, rod, ellipsoid, sphere, and cake-like morphologies have been successfully fabricated by using a surfactant-free hydrothermal method, in which the morphology of the BiVO4 microstructures can be tuned by simply varying the molar ratio of Bi(NO)(3).5H(2)O to NaVO3 in the starting materials. Based on a series of contrast experiments, the probable formation mechanism of the BiVO4 microstructures with multiple shapes have been proposed. The photocatalytic performances of the as-prepared BiVO4 microstructures have been evaluated by studying the degradation of Rhodamine B solutions under visible light irradiation. The results reveal that the cake-like BiVO4 microstructures exhibit the higher photocatalytic activity than other BiVO4 microstructures due to its high surface area and unique morphology. (C) 2017 Elsevier B.V. All rights reserved.