The modification of electrodeposited polyaniline film by subsequent electrodeposition of 4,4'-diaminodiphenyl sulfone (DDS) leads to a new material having nanostructure. The coated polymer films were treated with various pH solutions. The film adherent characteristics and surface morphology were studied using SEM. The electrochemically synthesized polyDDS revealed good redox behavior. The DDS was also polymerized by the chemical oxidation method using potassium persulphate. The polymer was characterized by UV-Vis and FTIR spectral studies. The formation of polymer through the N-H group was understood from the single N-H stretching vibrational frequency at 3459 cm(-1). The X-ray diffraction studies revealed the formation of nano sized (28 nm) crystalline polymer. The conductivity of the polymer was determined to be 1.07 x 10(-4) S.cm(-1). The solubility of the chemically polymerized powder was ascertained, and polyDDS showed good solubility in DMF and DMSO. (c) 2005 Wiley Periodicals, Inc.