Alternating linear and branched poly(m-p-anilines) and poly(m-p-p-anilines) have been synthesized via palladium-catalyzed amination reactions. Polymers were oxidized to radical cations either chemically or electrochemically. The presence of radical cations was manifested by the appearance of two and three new bands in the UV-vis-NIR spectra of poly(m-p-anilines) and poly(m-p-p-anilines), respectively. EPR spectra of frozen solutions of partially oxidized polymers confirmed the formation of high-spin states for all polymers studied.