In this manuscript, we demonstrated a facile route for the controllable design of “Fluorine (F)-doped carbon” (C/F)-treated TiO2 hollow spheres with mesoporous shells (MHTO-C/F). The fabrication of this distinct mesoporous hollow structures and the C/F coating could effectively improve the electrolyte permeability and architectural stability, as well as electrical conductivity and lithium ion mobility. As anticipated, MHTO-C/F has several remarkable electrochemical properties, such as a high specific reversible capacity of 252mAhg−1, outstanding cycling stability of more than 210mAhg−1 after 100 cycles at 0.5C, and good rate performance of around 123mAhg−1 at 5C (1C=168mAg−1). These properties are highly beneficial for lithium storage.