A novel nanocomposite comprising MWNTs and mixed-conducting polymeric components (electronic and ionic) is prepared, characterized and investigated as a support for platinum (Pt). Nanocomposite of MWNTs and poly (3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT–PSS) is prepared by in situ polymerization and characterized using Fourier–Transform infrared spectroscopy (FT–IR), thermogravimetric analysis (TGA) in conjunction with scanning electron microscopy (SEM). Atomic force microscopy (AFM) studies are also carried out to characterize the surface topography of MWNTs/PEDOT–PSS nanocomposite. X-ray diffraction (XRD) studies reveal that MWNTs/PEDOT–PSS nanocomposite provides better backbone for the improved dispersion of Pt as evidenced by the reduced Pt crystallite size over MWNTs/PEDOT–PSS nanocomposite compared to MWNTs. Electrochemical characterization studies performed with Pt/nanocomposite and Pt/MWNTs demonstrate the superior catalytic activity of Pt/nanocomposite under reduced Nafion loadings in relation to Pt/MWNTs. It is observed that mixed conducting nanoporous network of MWNTs/PEDOT–PSS composite structure promotes the catalytic activity of Pt by enhancing catalyst utilization.