A new lithium containing iron(III) phosphite, LiFe(HPO3)2, has been synthesized via a solvent-free, low temperature, solid-state synthesis route. The crystal structure of this material has been determined employing single-crystal X-ray diffraction, which indicates that the compound has a three-dimensional structure formed by isolated FeO6 octahedral units joined together via bridging HPO3 pseudopyramidal moieties. This arrangement leads to the formation of channels along all the three crystallographic directions, where channels along the a- and b-axes host Li(+) ions. The compound was further characterized by TGA, IR, and Mössbauer spectroscopic techniques. Additionally, it has been demonstrated that this phase is electrochemically active toward reversible intercalation of Li(+) ions and thus can be used as a cathode material in Li-ion cells. An average discharge potential of 2.8 V and a practical capacity of 70 mAh·g(-1) has been achieved as indicated by the results of cyclic voltammetry and galvanostatic charge-discharge tests.