Monoclinic BiVO 4 nanorods and nanoplates were synthesized via the CTAB/water/n-butanol/n-octane microemulsion-mediated hydrothermal process. The physical and photophysical properties of the as-prepared samples were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), Raman spectroscopy, and UV–vis diffuse reflectance spectroscopy (UV–vis). It was found that the ratio of H 2 O to CTAB in microemulsion played a key role in the morphology evolution of the products. The possible formation mechanism of BiVO 4 nanostructure with various morphologies was briefly discussed. The Raman results indicated that the symmetry distortions in the local structure of the synthesized BiVO 4 were affected by the morphology of the products. The bandgaps (E g ) of BiVO 4 nanorods and nanoplates are 2.45 and 2.38eV, respectively. The synthesized BiVO 4 nanoplates showed superior photocatalytic activity compared with BiVO 4 nanorods due to their higher degree of structural distortion, larger surface area, and thinness.