A new titanium (III) phosphite Ti-2(HPO3)(3), has been synthesized under hydrothermal conditions. The solid-state structure of this material was solved using single-crystal X-ray diffraction. The anionic inorganic skeleton has a three-dimensional structure, which is built up by TiO6 octahedral units linked together via bridging HPO3 pseudo pyramids, giving rise to tunnels along the three crystallographic axes. This new compound displays a high thermal stability limit of 625 degrees C. IR and Raman spectroscopies show the vibrational modes of the (HPO3)(2-) oxoanions. Electrochemical activity of this phase toward reversible insertion of Li ion was studied for the first time by galvanostatic charge-discharge measurements, an insertion host for reversible accommodation of Li+ was observed. (C) 2018 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.