V2O5 hollow nanospheres of average diameter ca. similar to 28 nm and hollow cavity size ca. 18 nm were prepared by using polymeric micelles as a soft template. Transmission electron microscope (TEM) and X-ray diffraction (XRD) analyzes have confirmed the hollow spherical morphology with crystalline shell structure. The V2O5 hollow particles were investigated as cathode materials for lithium intercalation in Li-ion batteries (LIBs). The nanostructured electrode delivers a high capacity of 181 mAhg(-1) with capacity retention of 92.6% after 50 cycles of charge/discharge at a rate of 0.5 C. Interestingly, the hollow particles based electrodes maintain the structural integrity even after subjecting to high current density 2000 Ag-1 (10 C) and show good cycling performance and electrode stability. The enhanced electrochemical behavior is attributed to nanosize effect coupled with hollow void space of V2O5 hollow particles that facilitates fast lithium intercalation/deintercalation. (C) 2012 The Electrochemical Society. [DOI: 10.1149/2.082205jes] All rights reserved.