Vanadium pentoxide (V2O5) nanofibers (NFs) with a thin carbon layer of 3-5 nm, which wrapped on V2O5 nanoparticles, and integrated multiwalled carbon nanotubes (MWCNTs) have been fabricated via simple electrospinning followed by carbonization process and post-sintering treatment. The obtained composite displays a NF structure with V2O5 nanoparticles connected to each other, and good electrochemical performance: delivering initial capacity of 320 mAh g(-1) (between 2.0 and 4.0 V vs. Li/Li+), good cycling stability (223 mAh g(-1) after 50 cycles), and good rate performance ( 150 mAh g(-1) at 2 A g(-1)). This can attribute to the carbon wrapped on the V2O5 nanoparticles which can not only enhance the electric conductivity to decrease the impendence of the cathode materials but also maintain the structural stability to protect the nanostructure from the corruption of electrolyte and the strain stress due to the Li-ion intercalation/deintercalation during the charge/discharge process. And, the added MWCNTs play the role of framework of the unique V2O5 coated by carbon layer and composited with MWCNT NFs (V2O5/C@MWCNT NFs) to ensure the material is more stable.