Vanadium pentoxide (V2O5) has received considerable attention owing to its potential application in energy storage with high specific capacity (294 mAh g(-1)). However, the development of V2O5 cathodes has been limited by the intrinsically low electrical conductivity and slow electrochemical kinetics resulting in a significant capacity decay. In this article, in order to overcome the issues, V2O5 nanospheres and multiwalled carbon nanotubes (MWCNTs) are used to fabricate layer-by-layer composited paper as the cathode, which is prepared via electrostatic interaction and vacuum filtration by alternating the positively charged V2O5 nanospheres and the negatively charged terminated MWCNT solutions. As a result, the V2O5 nanospheres are closely intercalated between the adjacent MWCNT layers leading to minimize the disadvantage voids and enhance the overall conductivity of the composited electrode, which exhibits an enhanced cycling durability as well as improved rate capability.