Highly crystalline monoclinic scheelite BiVO4 powders are synthesized from aqueous Bi(NO3)3 and NH4VO3 solutions over a wide range of pH by a hydrothermal process. BiVO4 powders with various morphologies, surface textures, and grain shapes are selectively synthesized by adjusting the pH. The dependence of the Raman peak position and intensity on the synthesis conditions indicates that the symmetry distortions in the local structure of the synthesized BiVO4 are affected by the preparation conditions. These variations in the local structure result in the modification of the electronic structure of BiVO4, which results in a blue-shift in the UV-vis absorption spectrum of hydrothermally synthesized BiVO4 in comparison with a well-crystallized sample prepared by homogeneous coprecipitation. The photocatalytic activities for O2 evolution from an aqueous AgNO3 solution under visible-light irradiation are strongly dependent on the pH used in the synthesis. The differences in the photocatalytic activities between BiVO4 samples prepared under various conditions is attributed to the degree of structural distortion, leading to differences in the mobility of photogenerated holes formed in the valence band, which consists of Bi 6s and O 2p orbitals.