Using cyclic voltammetry, Raman scattering and infrared (IR) spectroscopy, new findings concerning the electrochemical synthesis of composites based on multi-wall carbon nanotubes (MWNTs) and polypyrrole (PPY) doped with H 3 PMo 12 O 40 heteropolyanions are described in this report. To better understand the electrochemical mechanism behind the synthesis of these composites, the influence of the concentrations of pyrrole and the electrolytes of H 3 PMo 12 O 40 and H 2 SO 4 on the cyclic voltammogram profile is studied. The formation of PPY doped with H 3 PMo 12 O 40 heteropolyanions onto the MWNT surface is demonstrated by complementary studies of Raman scattering and IR spectroscopy.