Composite materials, containing fibrous VN nanoparticles and multiwalled carbon nanotubes (MWCNT) are prepared by a chemical method for application in electrochemical supercapacitors. We demonstrate for the first time that VN-MWCNT electrodes exhibit good capacitive behavior in 0.5 M Na2SO4 electrolyte in a negative voltage window of 0.9 V. Quartz crystal microbalance studies provide an insight into the mechanism of charge storage. Composite VN-MWCNT materials show significant improvement in capacitance, compared to individual VN and MWCNT materials. Testing results indicate that VN-MWCNT electrodes exhibit high specific capacitance at high mass loadings in the range of 10-30 mg cm(-2), good capacitance retention at scan rates in the range of 2-200 mV s(-1) and good cycling stability. The highest specific capacitance of 160 F g(-1) is achieved at a scan rate of 2 mV s(-1). The new findings open a new and promising strategy in the fabrication of hybrid devices based on VN. The proof-of-principle is demonstrated by the fabrication of hybrid supercapacitor devices based on VN-MWCNT negative electrodes and MnO2 - MWCNT positive electrodes with voltage window of 1.8 V in aqueous 0.5 M Na2SO4 electrolyte. The hybrid VN-MWCNT/MnO2-MWCNT supercapacitor cells show promising capacitive and power-energy characteristics. (C) 2014 Elsevier B.V. All rights reserved.