Composites based on polydiphenylamine (PDPA) doped with heteropolyanions of H3PW12O40 and single-walled carbon nanotubes (SWNTs) were prepared by electrochemical polymerization of diphenylamine (DPA) on carbon nanotube films deposited onto Pt electrodes. HRTEM studies reveal that the electrochemical polymerization leads to the filling the spaces between tubes which compose the bundles, creating a monolithic film on the Pt electrode. The resulting composites were tested as active materials in supercapacitors. Resonant Raman scattering studies showed that the electropolymerization of DPA in the presence of H3PW12O40 and SWNTs leads to the covalent functionalization of SWNTs with doped PDPA. The covalent functionalization of SWNTs with PDPA doped with H3PW12O40 heteropolyanions was revealed by FTIR spectroscopy, based on the changes in the vibrational features of PDPA and H3PW12O40. These changes included i) a down-shift of the PDPA IR bands, which was attributed to the C-H bending vibrational mode of benzene (B), C-aromatic-N, C-C stretching (B) + C-H bending (B) and C-C stretching vibrations of the B ring, from 1174, 1321, 1495 and 1603 cm(-1) to 1165, 1313, 1487 and 1599 cm-1, respectively; ii) a change in the peak positions of IR bands associated with the W = O and P-O-W vibration modes of H3PW12O40; and iii) a down-shift of the IR band situated in the spectral range 650-725 cm(-1), which was assigned to the inter-ring deformation vibration mode. The characterization of symmetric solid-state supercapacitors was performed for electrodes prepared from i) SWNTs functionalized with PDPA doped with H3PW12O40 heteropolyanions, ii) SWNTs electrochemically decorated with H3PW12O40 heteropolyanions, and iii). PDPA doped with H3PW12O40 heteropolyanions. Preliminary results indicate high discharge capacitance values of up to 157.2 mF/cm(2) for SWNTs functionalized with PDPA doped with H3PW12O40 heteropolyanions. The discharge capacitance of this material is superior to those recorded for SWNTs electrochemically decorated with H3PW12O40 heteropolyanions (similar to 18.2 mF/cm(2)) and PDPA doped with H3PW12O40 heteropolyanions (similar to 62.1 mF/cm(2)). (c) 2012 Elsevier B.V. All rights reserved.