Novel anatase titanium dioxide (TiO2) microspheres with exposed 0011 facets were successfully synthesized via a facile and controllable hydrothermal approach using sodium fluoroborate as the reagent. The products were characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), and X-ray photoelectron spectroscopy (XPS). XRD results showed that the TiO2 microspheres were anatase phase and had good crystallinity. SEM images showed that the as-prepared TiO2 samples displayed surface of microspheres with exposed 0011 facets and a mean diameter of 3.2 mu m Experimental results revealed that the as-prepared TiO2 microspheres might be assembled by nanosheets. The formation process of the TiO2 microspheres was preliminarily investigated.