Anatase TiO2 microspheres with a high percentage of exposed (001) facets were synthesized by a template-free hydrothermal method without using concentrated hydrofluoric acid. The influence of various experiment conditions, such as hydrothermal temperature, acid condition, reaction time, etc., on the morphology of the final products was investigated in detail. The formation mechanism of the microspheres was deduced according to the XRD, SEM, TEM, and HRTEM characterizations. The as-obtained microspheres exhibited superior photocatalytic activity in the degradation of Acid Red 88 compared to TiO2 without exposed (001) facet.