Bismuth vanadate catalysts were prepared at different pH values by hydrothermal method. The materials were characterized by BET, XRD, Raman, SEM, DRS, FT-IR and PL techniques. It revealed that the pH value of the precursor solution can influence significantly on the morphology and structure of the product. The photocatalytic activities of the samples were evaluated for the degradation of phenol in the presence of a small amount of H2O2 under natural sunlight. The BiVO4(2-100) sample prepared at pH 2 and 100 degrees C showed the highest percentage of phenol degradation (100%) and highest reaction rate (1.41 mg L-1 min(-1)) in 90 min. In addition, 95% TOC removal can be achieved. Monoclinic form of BiVO4 is found to be more effective for photodegradation. This high photocatalytic activity of BiVO4(2-100) sample is associated with the affluence of hydroxyl groups present on the catalyst surface, which can prevent the electron-hole recombination by trapping hole and generating of radicals acting as powerful oxidants. (C) 2014 Elsevier B.V. All rights reserved.