AbstractPoly(3,4‐ethylenedioxythiophene) (PEDOT) doped with a series of anionic polysaccharides such as carboxymethyl cellulose, sodium hyaluronate, xanthan gum, pectin, gellan gum were prepared by electropolymerization in aqueous solutions. Some other dopants of potassium nitrate, potassium sulfate, sodium poly(styrenesulfonate), and sodium polyacrylate were used in comparison with the anionic polysaccharides. The electrochemical properties and stability of the obtained PEDOT films were also investigated. It was found that indium tin oxide (ITO) conductive glass could be used as the working electrode of the electropolymerization of EDOT and that the dopant had a great influence on polymerization potential and overoxidation potential. These charged biomolecules of anionic polysaccharides were found to facilitate electropolymerization of EDOT instead of common doping anions as counterion. The electroactive PEDOT films doped with anionic polysaccharides showed stable electrochemical properties, good texture, and adhesion properties to the ITO conductive glass. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012