Hydrogen molybdenum bronze (HMB) is electrochemically deposited as a homogeneous shell to VO2 nanoflakes grown on graphene foam (GF), forming a GF+VO2/HMB integrated electrode structure. Asymmetric supercapacitors based on the GF+VO2/HMB cathode and neutral electrolyte are assembled and show enhanced performance with weaker polarization, higher specific capacitance and better cycling life than the unmodified GF+VO2 electrode. Capacitances of 485 F/g (2 A/g) and 306 F/g (32 A/g) are obtained because of the exceptional 3D porous architecture and conductive network. In addition, the GF+VO2/HMB electrodes are also characterized as the cathode of lithium ion batteries. Very stable capacities at rates up to 30 C are demonstrated for 500 cycles. This new type of shell material is expected to have its generic function in other metal oxide based nanostructures. ; ASTAR (Agency for Sci., Tech. and Research, S’pore) ; MOE (Min. of Education, S’pore)