Abstract 4, 4′-Diaminodiphenyl sulphone was polymerized (with lithium/cobalt/lithium–cobalt salts) by chemical oxidation method using potassium perdisulphate. The solubility of the chemically prepared polymer–metal nanocomposite was ascertained and it showed good solubility in DMF, chloroform, trichloroethylene and DMSO. The PDDS–Li/Co/Li–Co nanocomposites were characterized by UV–vis and FTIR spectral studies. Amine and imine vibrations observed at 1593 and 1503 cm −1 were shifted to lower wave numbers when the polymer–metal composites were formed. A single absorption peak due to the N–H stretching vibration of the imino groups of polymer–metal nanocomposite is observed around 3459 cm −1 and it suggests the participation of NH group during polymerization. The X-ray diffraction studies revealed the formation of nano sized (82 nm) crystalline polymer. The conductivity of the PDDS–Li–Co nanocomposite was determined to be 6.26 × 10 −2 S cm −1. SEM analysis showed mixed granular nature of the polymer–metal nanocomposite. The capacitance (159.04 μF) of chemically synthesized PDDS–Li–Co nanocomposite is suggested as a potential capacitive material.