The potentiodynamic synthesis and subsequent characterisation of a polyaniline (PAn) grown in the presence of a water-soluble conducting polymer, poly(2-methoxyaniline-5-sulfonic acid) (PMAS) is described. The novel polymer is obtained as a water-insoluble film consisting of a PAn backbone with PMAS integrated as the molecular dopant. The electrodeposition of the polyaniline material is enhanced by the presence of the electrically conducting PMAS polyelectrolyte dopant, which functions as a molecular template providing supramolecular pre-ordering as well as simultaneously facilitating charge transport during electrodeposition.