Multiwall carbon nanotube (MWCNT) powders were dispersed in distilled water and grafted with polystyrene sulfonate sodium salt (PSS-Na+) through radical polymerization under nitrogen gas purging, then protonated with HCl. The resultant was washed with the cosolvent of methanol and water. The grafting efficiency was characterized through Thermogravometric analysis (TGA). The weight loss by decomposition of poly(styrenesulfonic acid) (PSSA) was assumed to be the weight fraction of PSSA grafted on MWCNT. The powders were dried and dispersed in water using ultrasonication. Aniline monomer and ammoniumpersulfate (APS) were introduced for chemical oxidative polymerization. The electrochemical analysis of composite electrode was carried out using cyclic voltametry (CV). The composite represents excellent electrical conductivity and doping efficiency with polymeric dopant. Furthermore, doping effect of secondary dopant, sulfuric acid, was characterized by UV-Vis spectroscopy. The composite exhibits longitudinal morphology on which PANI wrapped MWCNT.