The (C3H6N6)(0.67)V2O5 hybrid nanorods are synthesized through the self-assembly of melamine organic molecules confined by V2O5 layers and used as cathode material in the lithium-ion battery. The prepared hybrid overcomes the irreversible structure puckering problem of LixV2O5 when excess Li+, x > 1, is intercalated. It demonstrates that layered oxides combined with selective organic moieties forming an ordered structure can significantly reduce the lattice stress and structure puckering problems during lithium intercalation/deintercalation process thereby extending their cycle reversibility in the wide potential range from 1.9 to 3.5 V and reaching to x = 2 of Li-x(C3H6N6)(0.67)V2O5. The hybrid material developed in this work tackles the structure puckering problem of V2O5 layers and opens the door for studying new battery system with greater ionic radii, such as Na+, Mg2+ and Al3+. (C) 2017 The Electrochemical Society. All rights reserved.