Hydrangea-like F-doped TiO2 microspheres have been synthesized on a large scale by a simple hydrothermal process using potassium titanium oxalate as the titanium source, ammonium fluoride and hydrogen peroxide as the etchant. The photocatalytic activities were evaluated using carbamazepine as the target organic molecule under UV and visible light irradiation. Structural characterization indicates that the hydrangea-like TiO2 microspheres, with an average diameter of 2.80 μm, are composed of numerous anatase TiO2 petals. Moreover, it is found that both the NH4F and H2O2 dosages have important effects on the formation of the hydrangea-like structures. In addition, photocatalytic experiments show that the hydrangea-like TiO2 microspheres calcined at 500°C exhibit high photocatalytic efficiency under both UV and visible light irradiation. The enhanced photocatalytic activity can be attributed to the successful fluorine doping, good crystallinity, and the unique nanostructures.