Conducting polypyrrole (PPy) films doped with p‐toluene solfonate (pTS−), perchlorate (ClO4−) and polyphosphate (PP−) were electrochemically synthesized on the stainless steel SS‐304 and the Indium Tin Oxide (ITO) glass substrates successfully. The conducting polymer composite films were studied by Fourier transform infrared spectra, integrated thermal analysis system and scanning electron microscopy, respectively. Four‐point probe measurements and in situ nanotribolab system equipped with a nanoscale electrical contact resistance package were employed to analyze their electrical and mechanical properties. Results indicate that the film doped with PP− ion showed the best thermal stability. For the ClO4− ion doped films, the glass transition occurred at 274.8 °C. The pTS− ion doped film on the SS‐304 steel had a good conductivity, and there was a voltage barrier that ranged from −1.25 to 1.9 V according to the current–voltage curves. Nanoindentation tests show that the mechanical properties of the PPy/pTS− film and the PPy/PP− film were better than that of PPy/ClO4− films. Copyright © 2012 John Wiley & Sons, Ltd.