For the first time, a one-step synthetic strategy has been developed towards the preparation of Ti3+ self-doped TiO2 with internal-pores and highly exposed {001} facets using ethylene glycol (EG) and HF as control agents. The obtained samples were characterized by XRD, XPS, SEM, TEM, HAADF-STEM, photoluminescence spectroscopy (PL), and UV-vis reflectance spectroscopy. The synergistic effect of EG and HF plays a vital role in the formation of synthesized TiO2 with Ti3+ self-doping, internal-pores and highly exposed {001} facets. As-synthesized TiO2 exhibit much higher activity than commercial P25 on photocatalytic degradation of phenol and the outstanding performance is attributed to the synergistic effect of Ti3+ doping, internal-pores, and facets heterojunction. (C) 2017 Elsevier B.V. All rights reserved.