A facile approach to functionalize carbon nanofibers [CNFs] with nanostructured polyaniline was developed via in situ mechanochemical polymerization of polyaniline in the presence of chemically treated CNFs. The nanostructured polyaniline grafting on the CNF was mainly in a form of branched nanofibers as well as rough nanolayers. The good dispersibility and processability of the hybrid nanocomposite could be attributed to its overall nanostructure which enhanced its accessibility to the electrolyte. The mechanochemical oxidation polymerization was believed to be related to the strong Lewis acid characteristic of FeCl3 and the Lewis base characteristic of aniline. The growth mechanism of the hierarchical structured nanofibers was also discussed. After functionalization with the nanostructured polyaniline, the hybrid polyaniline/CNF composite showed an enhanced specific capacitance, which might be related to its hierarchical nanostructure and the interaction between the aromatic polyaniline molecules and the CNFs.