Vanadium pentoxide (V₂O₅) is a promising electrode material for supercapacitors owing to its high theoretical capacitance, natural abundance and low cost. However, the low conductivity and electrochemical instability hinder its practical applications. Subjected to this challenge, core-shell structured V₂O₅/conducting polymers hybrid aerogels, V₂O₅/Poly(3,4-ethylenedioxythiophene (PEDOT), V₂O₅/Polyaniline and V₂O₅/polypyrrole, were synthesized in a versatile varient vaper-phase polymerization process and the resulting samples exhibited the enhanced electrochemical performances. Especially, V₂O₅/PEDOT aerogels delivered a high specific capacitiance of 614 F g^–1 and energy density of 85.3 W h/kg at the power density of 250 W/kg. After 50,000 cycles, V₂O₅/PEDOT presented a capacitance retention of 122% that suggests a capacity increase in the cycles. The excellent performances can be attributed to the robust conducting-polymer shell and valence varitation in V₂O₅. This effective stratagy pave a way to develop the high-performance electrode materials for supercapacitors.