Nanostructured epsilon-VOPO4 particles, synthesized by the thermal decomposition of H2VOPO4 have a diameter of 150 nm and a length up to 100 nm. Nanostructuring the material allows access to both the 4 V and 2.5 V redox potentials with an overall capacity approaching 200 mAh/g over 50 cycles. The structure of the epsilon-VOPO4 and its changes were investigated by X-ray diffraction and electron microscopy, and its electrochemical behavior through constant current cycling and cyclic voltammetry. (C) 2013 The Electrochemical Society. All rights reserved.