Hierarchical Cu4V2.15O9.38 micro-/nanostructures have been prepared by a facile "forced hydrolysis" method, from an aqueous peroxovanadate and cupric nitrate solution in the presence of urea. The hierarchical architectures with diameters of 10-20 µm are assembled from flexible nanosheets and rigid nanoplates with widths of 2-4 µm and lengths of 5-10 µm in a radiative way. The preliminary electrochemical properties of Cu4V2.15O9.38 have been investigated for the first time and correlated with its structure. This material delivers a large discharge capacity of 471 mA h g(-1) above 1.5 V, thus making it an interesting electrode material for primary lithium ion batteries used in implantable cardioverter defibrillators.