Polyaline(PANI) films doped with dodecyl benzene sulfonic acid (DBSA) were polymerized by cyclic voltammetry on gold-plated PET films. To research the effect of acid concentration and polymerization cycle on PANI, infrared spectra, micro morphology, cyclic voltammetry curves, X-ray diffraction patterns and UV-vis-NIR reflection spectra were measured respectively. Results show that DBSA- could incorporate into PANI molecular chains, which lead to form PANI fibers by compatibilization of long-chain alkyl in DBSA-. In polymerization progress, the polymerization rate increased as DBSA concentration increasing, which lead to flaky dense structure, high degree of crystallinity, large ion steric hindrance and low spectral reflectance. With the increase of polymerization time, surface morphology of PANI becomes worse and appears clusters phenomenon, nucleation rate gradually increase and fibers grow laterally into bands.