The self-assembled hierarchically flower-like FeWO4 microcrystals have been synthesized by a simple hydrothermal method. The microstructure and electrocatalytic properties of synthesized FeWO4 nanoflakes are characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray (EDS), transmission electron microscopy (TEM), and electrochemical techniques. The hierarchically flower-like FeWO4 nanoflake provide adequate amount of active component for the lithium storage, resulting in a high lithium storage capability for the present system. The hierarchical structure of the 2-dimensional nanoflake is capable to mediate the massive volume expansion and contraction during lithiation and delithiation processes. This is probably the reason for the enhancement of the electrochemical performance of the FeWO4 nanoflake structure based electrode. Copyright (C) 2014, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.