Efficient electrode material of Na-V2O5-reduced graphene oxide (rG-O) nanocomposite is synthesized by the restacking of anionic component nanosheets with Na+ ions at room temperature. The restacked Na-V2O5-rG-O nanocomposite shows layer-by-layer-ordered structure of V2O5/rG-O nanosheets and Na+ ions with mesoporous stacking structure and expanded surface area. Upon the restacking with rG-O, the pentavalent V5+ oxidation state and layered lattice of vanadium oxide nanosheet remain unchanged. The composite formation with rG-O leads to a significant enhancement of the discharge capacity from 50 to 150 mAh g(-1) as cathode material for Na-ion batteries, underscoring the usefulness of restacking between metal oxide and rG-O nanosheets in exploring novel nanocomposite electrode materials. (C) 2016 Elsevier B.V. All rights reserved.