Vanadium oxide films composed of porous walnut-like particles are fabricated by electrostatic spray deposition (ESD) with an oil-bathed suspension precursor. The micron-sized particles are constructed from vanadium oxide nanocrystals of size around 50-100 nm and the valence of vanadium is determined by electron energy loss spectroscopy (EELS). As a cathode material for rechargeable lithium batteries, it exhibits stable reversible specific capacity and ultra-high rate capability. It delivers a specific discharge capacity of 254 mAh g(-1) in first cycle, and still maintains 200 mAh g(-1) after 100 cycles in the voltage range of 2.1-4.0 V. When the cell is cycled between 2.5 and 4.0 V, its discharge capacity reaches 103 mAh g-1 at 50 C and reserves 85 mAh g(-1) at 10 C even at 10 degrees C. (C) 2012 Elsevier B.V. All rights reserved.