The initial formation of poly(aniline) and its derivatives was investigated for the electropolymerization of anilines in several non-aqueous solutions without proton donor to prepare the films effectively. In this study, 1,2-dichloroethane, acetonitrile, propylene carbonate and tetrahydrofuran were employed as solvent. The donor number of the solvent affects the deprotonation of the cation radical of the monomer formed, and the dimer and products, and the dielectric constant of the solvent affects chain propagation during the electropolymerization of anilines respectively. 1,2-Dichloroethane is revealed to be a more effective solvent than the others used in this study to prepare electroactive and soluble poly(aniline)s with head-to-tail structure.