In this work, poly(2-fluoroaniline), poly(2-chloroaniline), poly(2-methylaniline), and poly(N-ethylaniline) were prepared by a self-assembly method using an oxidizing system consisting of a dopant anion, p-toluene sulfonate with ammonium peroxydisulfate. The effects of substituents on the surface morphology, conductivity, molecular weight, spectral and thermal properties of the polymers were studied. SEM results revealed that the surface morphology of the resulting polymers changed from nanofiber to spherical structure by changing the substituents on the aniline monomers. The structure and properties of these conducting films were characterized by FTIR, UV-vis, elemental analysis, TGA, conductivity, and cyclic voltammetry. The polymer films show electroactivity in monomer free solution. Molecular weight of the polymers was determined by gel permeation chromatography. The dry electrical conductivity values of the substituted-polyanilines were found to be lower than that of PANI. The results revealed that the molecular structures of the polymers were similar to those of the emeraldine form of polyaniline. (C) 2009 Wiley Periodicals, Inc. J Appl Polym Sci 115:3024-3030,2010