The redox process undergone by the electrochemically synthesized poly (2,2'-dithiodianiline), poly (DTDA), has been examined in acetonitrile-water mixtures by electrochemical and spectroscopic techniques. The spectroscopic properties of this material are equivalent to those exhibited by the chemically synthesized one. The polymeric structure displays a ladder structure, with S-S bonds serving as interconnections between two adjacent polyaniline chains. The kinetic reversibility of the RS-SR -> 2RS(-)reaction is very poor for the DTDA monomer species, and this irreversibility is retained in the polymeric material. According to the results presented, the hypothesis that poly (DTDA) could display a high energy density due to the simultaneity of the leucoemeraldine -> emeraldine and dithiolate -> disulfide electrochemical transformations does not seem justified. (c) 2006 The Electrochemical Society.