A series of poly(o-/m-toluidine-co-o-/m-aminoacetophenone) copolymers combining the features of high conductivity and processibility are synthesized and characterized by a number of techniques including H-1 NMR; thermogravimetry; IR, Raman, and UV-visible spectroscopy; scanning electron microscopy; and X-ray diffraction. The copolymers are synthesized by the emulsion and inverse emulsion methods using conventional ammonium persulfate and a new oxidant, benzoyl peroxide, respectively. The influence of the polymerization conditions such as the monomer feed ratios, solvent, and the nonsolvent is investigated. The composition of the resulting copolymers is determined by H-1 NMR analysis. The conductivity of the copolymers varies with the aminoacetophenone content in the feed and the polymerization conditions. It is interesting that the conductivity of the copolymers is higher than that of the corresponding homopolymers. The results are rationalized on the basis of the effect of the -COCH3 substituent on the polymer structure. (C) 2004 Wiley Periodicals, Inc.