The interfacial interaction and orientation of molecules during the polymerization process plays a vital role in the enhancement of the surface properties of conducting polymers. In this perspective, a solid-phase mechanochemical route is employed to prepare poly(2,5-dimethoxy aniline) (PDMA) and its salts with superior properties. Various studies performed on the as-prepared polymer highlights the formation of polymeric particles with excellent physicochemical properties. Elemental analysis showed the presence of dopants anion in the polymeric backbone. Spectroscopic profile of PDMAs revealed the formation of emeraldine form of PDMAs. Moreover, these studies indicate the formation of PDMA-HCl in a highly doped state. The surface morphological pictures of PDMAs revealed the formation of aggregated microstructured to nanostructured particulates. X-ray diffraction, cyclic voltammetry were used to evaluate the physicochemical properties of PDMAs. PDMA salts exhibited crystalline behavior and good electrochemical activity. TG/DTA analysis showed that all the PDMAs were thermally stable up to 240 degrees C. (C) 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012