BiVO4 hierarchical structures were synthesized by means of a surfactant free hydrothermal method having good photoactivities for the degradation of Methylene Blue and Rhodamine B under UV-vis irradiation. From the structural and morphological characterization it has been stated that BiVO4 present the monoclinic crystalline phase with different morphologies depending on the pH value. For Methylene Blue the photodegradation rate is strongly affected by the crystallite size and higher (0 0 4) facet exposition. On the contrary, for Rhodamine B, the zeta-potential of the surface clearly determines the photocatalytic performance of BiVO4 catalyst. (C) 2013 Elsevier B.V. All rights reserved.