Monoclinic BiVO4 (m-BiVO4) microThanostructures, such as nanorods, nanofibers, bundle-like nanostructures, and porous submicrometer-sized rods, have been successfully synthesized by a facile solvothermal method in an ethylene glycol-water-sodium oleate system. The morphologies and sizes of m-BiVO4 micro/nanostructures can be controlled by adjusting the synthetic parameters, such as the concentrations of sodium oleate and reaction time. Among them, the synthesized m-BiVO4 nanorods have rectangular cross sections, and can grow along the [001] direction, and are enclosed by well-defined facets, such as (002), (240), and ((2) over bar 10), which are distinct from that with circular cross sections. A crystallization-cleavage-disassembly process has been proposed for the formation of m-BiVO4 nanorods with rectangular cross sections. The photocatalytic activity of m-BiVO4 nanostructures is affected greatly by the sizes and shapes of m-BiVO4 nanostructures. Photocatalytic measurements show that the m-BiVO4 nanorods with rectangular cross sections exhibit higher photocatalytic activities of Rhodamine B in comparison with m-BiVO4 nanofibers with circular cross-sections and porous submicrometer-sized rods. (c) 2012 Elsevier Ltd. All rights reserved.