Vertically aligned polyaniline nanowhiskers (PANI-NWs) doped with (1R)-(−)-10-Camphorsulfonic acid (L-CSA) have been successfully synthesized on the external surface of ordered mesoporous carbon (CMK-3) by chemical oxidative polymerization. The specific surface area of the PANI-NWs/CMK-3 nanocomposite remains as high as 497m 2 g −1 by removing mesoporous silica template after the polymerization of aniline. Structural and morphological characterizations of the nanocomposite were further investigated by XRD, FTIR and FE-SEM measurements. The result shows that the nanocomposite with 40wt% PANI applying in supercapacitor devices possesses a large specific capacitance of 470Fg −1 and good capacitance retention of 90.4% is achieved after 1000 cycles at a current density of 1.0Ag −1 . The synergistic effect of small PANI nanowhisker arrays and well-ordered mesoporous carbon endows the composite with high electrochemical capacitance and good cycling stability.