We report on the synthesis and electrochemical properties of leucoemeraldine base, emeraldine salt and pernigraniline base forms of polyaniline (PAN!) in the form of nanocomposites with MWNTs. The oxidation state of PANI in the composite is controlled by doping and dedoping of the emeraldine salt form of PANI/MWNT composite, which is prepared through chemical polymerization, using oxidizing and reducing agents without changing the morphology of PANI in the composite and is confirmed by ultraviolet-visible spectroscopy (UV-vis) spectroscopy and Fourier transform infrared (FT-IR) spectroscopy. The electrochemical and pseudocapacitive properties of the composites are investigated using cyclic voltammetry and analyzed with respect to the oxidation state of polyaniline. The PANI/MWNT nanocomposites show specific capacitance values of 217 Fg(-1) 328 Fg(-1) and 139 Fg(-1) for leucoemeraldine base, emeraldine salt and pernigraniline base, respectively. Electrochemical impedance spectroscopy is performed to explain the different electrochemical properties of PANI in different oxidation states. (C) 2011 Elsevier B.V. All rights reserved.