Nano-sized hexagonal WO3.0.33H(2)O/C is prepared by the solution combustion synthesis & hydrothermal method. This material has been used as the anode for high performance lithium-ion batteries for the first time. Carbon layer is uniformly coated on hexagonal WO3.0.33H(2)O nanoparticles. The samples are characterized by X-ray diffraction (XRD), thermal analysis (TG-DSC), Raman spectra, scanning and transmission electron microscopy (FESEM and TEM). Electrochemical properties are studied by cyclic voltammetry and galvanostatic charge/discharge cycling. Prepared WO3.0.33H(2)O/C electrode shows high and reversible capacity of 768 mAh g(-1) after 200 cycles at 100 mA g(-1), which is higher than the reported orthorhombic WO3.0.33H(2)O. The specific structure can provide efficient channels for transporting Li+ swiftly. Therefore, hexagonal WO3.0.33H(2)O/C shows a great potential as the anode material for lithium-ion batteries. (C) 2016 Elsevier B.V. All rights reserved.