An efficient enzymatic route for the synthesis of conducting oligomer of substituted aniline complexed with poly(sodium 4-styrenesulfonate) is presented. This polyelectrolyte assisted horseradish peroxidase catalyzed oligomerization of ortho-toluidine provides a route to synthesize water-soluble, highly conductive oligomers under acidic conditions. The UV-Vis, FTIR, thin film conductivity, molecular weight assessment and modeling studies of the oligomer/polymer complex indicate the presence of a thermally stable and electroactive oligomer with extended conjugation that was not present in similar conductive polymers (e.g. PANI). Moreover, the use of water-soluble templates provide a unique combination of properties such as high conductivity and processability. The same procedure was also implemented for the polymerization of 2,6-xylidine: however, the reaction did not occur suggesting a much more complex stereo-specificity of the enzymatic polymerization. Modeling studies were used to explain this behavior. The conductive poly(ortho-toluidine) can be used in chemiresistive sensors for the detection of humidity.