3D flower-like (NH4)0.83Na0.43V4O10·0.26H2O vanadium bronze nano-platelet clusters are prepared via a facile hydrothermal method. The thickness of the nano-platelet is around 50nm and the length ranged up to several micrometers. When used as positive electrode in rechargeable lithium battery, this material exhibits good cycle stability at different discharge rates (0.18–0.67C rate) and voltage limits (1.5–3.4V and 2.0–3.4V). The improvement the electrochemical properties of the (NH4)0.83Na0.43V4O10·0.26H2O might be attributed to the change of the lattice parameters due to the co-intercalation of the superstoichiometric cations (Na+ and NH4 +).