We present herein a facile two-step chemical vapor deposition (CVD) approach to synthesize carbon nanotube (CNT) supported vanadium oxide nanosphere nano-composite hetero-structures as electrochemical supercapacitors. The high electronic conductivity of CNTs has been exploited to provide a 3-D electron transport medium on which vanadium oxide nano-droplets interact with electrolyte to exhibit excellent supercapacitor behavior in aqueous media. Thin nano-scale droplets of vanadium oxide deposited on the CNTs exhibit excellent capacitance values as high as 1400 Fg(-1) with good rate capability and excellent charge retention up to 200 cycles. The electrochemical mechanisms and materials properties responsible for the supercapacitor properties of CNT supported vanadium oxide have been discussed at length. (C) 2013 The Electrochemical Society. All rights reserved.