High photocatalytic efficiency, easy recovery, and no biological toxicity are three key properties related to the practical application of anatase photocatalyst in water cleaning, but seem to be incompatible. Nanoparticles-constructed hierarchical anatase microspheres with high crystallinity and good dispersion prepared in this Study via one-step solution processing at 90 degrees C under atmospheric pressure by using ammonium fluotitanate its the titanium source and urea as the precipitant can reconcile these three requirements. The hierarchical microspheres were found to grow via ail aggregative mechanism, and contact recrystallization occurred at high additions of the FeCl3 electrolyte into the reaction system. Simultaneous incorporation of fluorine and iron into the TiO2 matrix was confirmed by combined analysis of X-ray diffraction, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, and UV-vis absorption spectroscopy. Surface structure and morphology changes of the microspheres induced by high-temperature annealing were clearly observed by field-emission scanning electron microscopy, especially for the phase-transformed particles. The original nanoparticles-constructed rough surfaces partially became smooth, resulting in a sharp drop in photocatalytic efficiency. Interestingly, iron loading has detrimental effects oil the visible-light photocatalytic activity of both the as-prepared and the postannealed anatase microspheres but greatly enhances the photocatalytic activity of the as-prepared anatase microspheres Under UV irradiation. No matter under UV or visible-light irradiation, the fluorine-loaded anatase microspheres and especially the postannealed ones show excellent photocatalytic performance. The underlying mechanism of fluorine and iron loading oil the photocatalytic efficacy of the anatase microspheres was discussed in detail, Beyond photocatalytic applications, this kind of material is of great importance to the assembling of photoactive photonic crystal that call control light motion.