Electrochemical properties of various TiO2 polymorphs, anatase (A-TiO2), rutile (R-TiO2), and columbite (C-TiO2), were examined as a negative electrode material for lithium-ion batteries, to clarify the relation between the crystal structures and electrochemical activities of TiO2 polymorphs. Here, the C-TiO2 sample was synthesized by a high-pressure method under 12 GPa, and crystallized into an orthorhombic structure with the Pbcn space group. Furthermore, both C-TiO2 and R-TiO2 adopt distorted hexagonal-close-packed arrays of O-2-ions, which have been empirically related to the electrochemical inactivity of lithium insertion materials. Surprisingly, the C-TiO2/Li cell exhibited stable discharge and charge profiles with a rechargeable capacity (Q(recha)) of similar to 70 mAh center dot g(-1). Evaluating Q(recha) and cyclability revealed that the electrochemical performance of C-TiO2 is superior to those of A-TiO2 and R-TiO2. The comparison of the crystal structures between C-TiO2 and R-TiO2 indicated that the conduction pathway for Li+ ions is crucial to the electrochemical properties of TiO2 polymorphs. (c) 2017 The Electrochemical Society. All rights reserved.