Vanadium Pentoxide (V2O5) has been identified as a potential cathode material owning to its high specific capacity, theoretically, 441 mAh g-1 for 3Li+ ions insertion/extraction and 294 mAh g-1 for 2Li+ ion insertion/extraction. However, the intrinsic drawbacks of V2O5, i.e. structural instability and poor electric and ionic conductivity, greatly inhibit the access of full capacity as well as the cycling and rate performance of this material. Here, we report a CTAB-assisted hydrothermal reaction to synthesize V2O5 clusters with nanofeatures. Unique porous fiber structure was obtained by assembly of tiny V2O5 nanoparticles, however, the fibers were aggregated into unfavorable bundles after thermal annealing. To achieve a dispersed structure and increase the conductivity, nitrogen-doped Graphene (NG) suspended in ethylene glycol was added to the reactant mixture. The obtained spherical V2O5 particles have similar assembled nanofeatures, and NG sheets are randomly intercalated into the matrix of V2O5 spheres. As cathode material in lithium ion battery, the V2O5/NG hybrids perform 2Li+ ion storage and demonstrate better cycling and rate performance compared to the bundle-like V2O5 fibers, delivering higher specific capacity of around 300 and 150 mAh g-1 at a rate of C/10 and 5C, respectively. The enhanced performance in electrical energy storage are attributed to the synergistic effect of the nanostructured V2O5/NG composites.