Fe-doped TiO2 nanoparticles with highly exposed (0 0 1) facets are directly synthesized from Ti-bearing tailings by a facile method for the first time. The effects of F-based additive on the decomposition rate of Ti-bearing tailings as well as exposure percentage of (0 0 1) facets are systematically investigated in this work. The results demonstrate that F-based additive agent effectively promotes decomposition of Ti-bearing tailings during the acidolysis process. What's more, F-based additive agent also plays a key role in the exposure of high-energy (0 0 1) facets for the obtained TiO2 nanoparticles. Synthesized F-drived TiO2 nanoparticles present outstanding photocatalytic activity on pollution degradation under visible and UV light. This study demonstrates a promising way to achieve advanced materials from secondary resources.