Rhodamine 6G and Azure B substituted polyanilines are prepared by oxidative polymerization of aniline in an aqueous acidic media using hippuric acid and tosic acid as dopant and ammonium per sulphate as oxidant. Substitution of rhodamine 6G and azure B on polyaniline backbone takes place in presence of butyl lithium. The structures of rhodamine 6G and azure B substituted polyanilines was elucidated by UV–visible spectroscopy, IR spectroscopy,1H nuclear magnetic resonance (1H NMR), 13C nuclear magnetic resonance (13C NMR). Molecular weight and specific surface area were determined by gel permeation chromatography (GPC) and Brunauer–Emmett–Teller (BET) analysis. Conductivity of rhodamine 6G and azure B grafted polyanilines were computed by two probe conductometer.