A biometic route for synthesis of a conducting molecular complex between polyalkoxyanitines and a polyelectrolyte, poly (sodium 4-styrenesulfonate)(SPS) is presented. Horseradish peroxidase (HRP) was used to catalyze the polymerization of alkoxyanilines. A few of water-soluble ring-substituted polyalkoxyanilines have been enzymatically synthesized with variation of groups, such as ortho-methoxy, meta-methoxy, ortho-ethoxy, and meta-ethoxy to forrn polyalkoxyanilines/SPS complexes. The presence of alkoxy substituents affects the polymerization reactions. These enzymatic oxidation reactions occur in a different potential range to that observed for the chemical polymerization. Similar electrochernical and optical properties were obtained for every pair of ortho- and meta-alkoxy substituted polyanihnes. For comparing, polyalkoxyanilines were also prepared by chemical polymerization in the presence of SPS. (c) 2006 Wiley Periodicals, Inc.