A high molecular weight poly(2,2′-dithiodianiline) (PDTDA) was chemically synthesized by simple solution polymerization method. The weight average molecular weight ( M ̄ w ) was observed to be 420,000 by GPC analysis. The chemical structures of the undoped and the doped PDTDA were characterized by UV-Vis spectroscopy. It was confirmed that the SS bonds within repeating units could be conserved well after polymerization and doping process by FTIR spectroscopic analysis. The PDTDA powders were found to have granular structure and the average particle size was 1μm. The charge–discharge behavior of the Li/liquid electrolyte (1M LiPF6 in EC–PC)/PDTDA cell was also investigated with cycles.