ABSTRACTPreparation of electrically conducting polymer film with homogeneity is very important work for electrical and electronic applications. In order to make homogenous conductive polyaniline film, we selected water soluble glycopolymer (GP), as dopant for polyaniline. Pendant carbohydrates water soluble glycopolymer architectures, such as, homo, 3 and 4 multi‐armed polymers were prepared from methacryl‐2,3,4,6‐tetra‐O‐acetyl‐D‐glucopyranoside (MTAGP) monomer and EBrIB and 3‐ and 4‐aremed initiators via ATRP polymerization followed by deacetylation process. This water soluble glycopolymer was used as dopant for polyaniline salt via the chemical oxidative emulsion polymerization of aniline using glycopolymer and surfactant by ammonium persulfate oxidant. Sulfate and dodecylhydrogen sulfate (DHS) groups are doped on polyaniline system via protonating H+, whereas, glycopolymer involves on polyaniline through hydrogen bonding (PANI‐DHS‐SA‐GP). Coated film of PANI‐DHS‐SA‐GP salt showed resistance in ESD range. PANI‐DHS‐SA‐GP showed fluorescence and Hydrophilicity. Electrochemical performance of PANI‐DHS‐SA‐GP as electrode material in supercapacitor cell was found from charge–discharge measurement. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019, 136, 48043.