In this work, uniform InVO4 hierarchical microspheres with the assistance of sodium dodecyl benzene sulfonate (SDBS) have been successfully synthesized by a facile hydrothermal method. X-ray diffraction, X-ray photoelectron spectra, scanning electron microscopy, transmission electron microscopy, high-resolution transmission electron microscopy, and selected area electron diffraction were used to characterize the as-synthesized samples. The results indicate that such 3D hierarchical architecture InVO4 microspheres are polycrystalline and assembled by numerous nanocrystals. Nitrogen adsorption-desorption measurement and the pore size distribution curve suggest that mesopores exist in these hierarchical microarchitectures. The formation mechanism has been proposed based on Oswald ripening and nonoriented attachment. It is further found that SDBS plays a key role in the formation process, and when the amount of SDBS is adjusted, the average diameter of such InVO4 microspheres could be controlled from 5 to 1 mu m. UV-vis diffuse reflectance and PL spectra are employed to estimate the photoluminescence property of as-prepared InVO4 samples.