Bismuth vanadates (BiVO4) with various crystal structures (tetragonal scheelite, monoclinic scheelite, and tetragonal zircon) and morphologies (sphere-, nanosheet-, dendrite-, and flower-like) were controllably fabricated by using amild additive-free hydrothermal treatment process under the different preparation conditions. The crystal structures, morphologies, and photophysical properties of the products were well-characterized. Subsequently, their UV- as well as visible-light photocatalytic performance was evaluated via dyes rhodamine B (RB) and methylene blue (MB) degradation. Special attention was paid to evaluate the correlation of the reactivity with crystal structure, morphology, and electronic structure of as-prepared BiVO4 samples. (C) 2009 Elsevier B.V. All rights reserved.