Multichannel carbon nanofibers-based amorphous vanadium (VMCNFs) was fabricated via electrospinning technology and calcination process. The amorphous V2O5 were homogeneous dispersed in the carbon nanofibers with inner hollow channels. One-dimensional structure nanomaterials with a compound inner fistulous pore construction promote the electrochemical property due to the synergistic effect between the hollow inner channels and carbon nanofibers with amorphous vanadium. With changing the addition amount of PS acting as a porogen, the optimized VMCNFs-0.5, in which the molar ratio of VO(acac)(2)/ styrene monomer (SM) was 0.5, exhibited a high specific capacitance of 739 F g(-1) at 0.5 A g(-1) and good cycling performance with 80.3% capacitance retention after 1500 cycles. Thus this novel method can provide an acceptable idea for practical applications in energy storage. (C) 2016 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.