We have successfully demonstrated the reversible electrochemical Li-insertion properties of electrospun vanadium pentoxide nanofibers (VNF) in full-cell assembly with a Li4Ti5O12 anode. Li-insertion in to VNF is restricted for the intercalation of 1 mol of Li by adjusting lower cutoff potential (2.5-4 V vs Li). The half-cell (Li/VNF) delivered a reversible capacity of ~148 mA h g(-1) with excellent cycleability and capacity retention of over 85% after 30 cycles. Full-cell assembly is conducted for such VNF cathodes after the electrochemical lithiation (LiV2O5) with spinel Li4Ti5O12 anode under the optimized mass loadings. Full-cell (LiV2O5/Li4Ti5O12) delivered an excellent cycleability irrespective of applied current densities with good reversible capacity of ~119 mA h g(-1) (at 20 mA g(-1) current density). This work clearly demonstrates the possibility of using LiV2O5/Li4Ti5O12 configuration for high power applications such as hybrid electric vehicles and electric vehicles in the near future.