The primary aim of this work was to synthesize aligned perchloric-acid-doped poly(aniline) (HClO4-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 (X R D), 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 HClO4-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 HClO4-doped PANI nanotubes exhibit better electrode performances than their commercial counterparts because they possess more sites, higher conductivity, and relative flexibility. This indicates that HClO4-doped poly(aniline) nanomaterials are promising in the application of lithium/polymer rechargeable batteries.