Microspheric and lamellar BiVO4 powders were selectively prepared through a hydrothermal process by using cetyltrimethylammonium bromide (CTAB) as a template-directing reagent. The as-prepared BiVO4 powders were characterized by X-ray diffraction, electron microscopy, nitrogen adsorption-desorption experimentation, Fourier transform infrared spectrometry, and UV-vis diffuse reflectance spectroscopy. Experimental results indicate that microspheric BiVO4 with particle sizes in the range of 7 similar to 12 mu m can be derived from a relatively low hydrothermal temperature (<= 160 degrees C) and possess a mixed crystal consisting of tetragonal and monoclinic phases, whereas lamellar BiVO4 with a pure monoclinic phase can be obtained at a higher hydrothermal temperature (200 degrees C). Their photocatalytic activities for O-2 evolution were investigated by using Fe(NO3)(3) as a sacrificial reagent under visible-light irradiation, and the lamellar BiVO4 shows a better photoactivity than the microspheric product due to its pure monoclinic crystal phase. Moreover, the effects of CTAB content on the morphologies and crystal phases of the obtained products were also discussed. It was found that the addition of CTAB can adjust the morphologies of BiVO4 and obstruct the crystal phase transformation from the mixed crystal to pure monoclinic BiVO4 during the hydrothermal process.