The primary aim of this work was to synthesize aligned perchloric-acid-doped poly(aniline) (HClO(4)-doped PANI) nanotubes by a simple alumina template method and to investigate their application in lithium/poly(aniline) rechargeable batteries. Powder X-ray diffraction analysis (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and Fourier transform infrared (FTIR) analysis were used to characterize the nanostructures obtained. The second aim addressed the preparation of HClO(4)-doped PANI microspheres and nanofibers on a large scale through a modified spraying technique, since the template synthesis has limitations in mass production. The present synthesis methods are simple and can be extended to the preparation of a broad range of one-dimensional conductive polymers. Furthermore, electrochemical measurements showed that the as-prepared HClO(4)-doped PANI nanotubes exhibit better electrode performances than their commercial counterparts because they possess more active sites, higher conductivity, and relative flexibility. This indicates that HClO(4)-doped poly(aniline) nanomaterials are promising in the application of lithium/polymer rechargeable batteries.