A hierarchically structured free-standing V2O5/vertically aligned carbon nanotube/graphene foam (V2O5-VA-CNTs/GF) coated by PEDOT was designed. Instead of forming a thick coating layer around, the V2O5 nanobelts disperse uniformly among the CNTs forest without severe aggregations. The PEDOT-V2O5-VA-CNTs/GF delivered a reversible capacity of 296.8 mAh g(-1) at 1C, and has capacity retention of 113.3 mAh g(-1) at 5C after 1000 cycles. First principles calculations indicate the addition of VA-CNTs to V2O5 electrode could improve the electronic conductivity and facilitate Li-ion adsorption, which lead to the outstanding Li-ion storage and conversion behaviour.