An improved liquid phase deposition (LPD) method was developed to prepare the TiO2 microspheres with enhanced crystallinity in this study. The as-prepared samples were analyzed by X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), nitrogen adsorption and desorption instrument, as well as the UV-Vis absorption spectroscopy. The results showed that the samples prepared at various precursor concentrations were identified as the well-crystalline anatase TiO2 exposed with reactive {0 0 1} facets, which was caused by the introduction of fluorine during the hydrolysis process of (NH4)(2)TiF6 precursor solution. Moreover, with increased concentration of precursor solution, the dissolution of {0 0 1} facets occurred and the typical hollow spherical structure was also found. The photocatalytic experiments revealed that the as-prepared anatase TiO2 microspheres exhibited an effective photocatalytic activity during the process of Rhodamine B (RhB) degradation. (C) 2015 Elsevier B.V. All rights reserved.