Crystalline vanadium pentoxide with hierarchical mesopores was synthesized by using a CTAB/BMIC cotemplate (CTAB = cetyltrimethylammonium bromide, BMIC = 1-butyl-3-methylimidazolium chloride). The material was fully characterized by SEM, TEM, N2 adsorption-desorption, XRD, XPS, and CV methods. By elaborate adjustment of the template proportions, the distribution and size of the hierarchical pores were tuned successfully. CTAB cationic surfactant contributed more to the larger mesopores, whereas BMIC ionic liquid was beneficial in forming the smaller nanopores. The vanadium-containing anions combined with CTA+ micelles and BMI+ rings through electrostatic interactions. The CTA(+)-O(VO)O(-)-BMI(+) entities built up an orderly array, which finally formed the hierarchical mesoporous framework during thermal treatment. The mesoporous vanadium pentoxide directed by the cotemplate of CTAB/BMIC = 1:1 showed many orderly crystalline structures and demonstrated a large capacitance (225 F g(-1)); it is thus a promising material for electrochemical capacitors. Two alternative solutions to the disappearance of capacitance due to insertion of K+ are proposed in view of possible future applications.