62The films of polyaniline (PAn) have been synthesized by potentiodynamic oxidation of aniline (An) in aqueous solution of 0.5 MH2SO4 at the electrodes of amorphous metal alloys (AMA) of the composition Al87Ni8(REM)5, where REM≡Y, Ce, Gd, and Dy, as well as polycristalline aluminum. The process of electrochemical oxidation of An on AMA-electrodes was analyzed and compared with the process of An’s oxidation on the polycrystalline Al-electrode. It was established that the difference in the form of cyclic voltammogramms is conditioned by the presence of amorphic components in the AMA composition, which cause of different resistance of surface oxide films on the working electrodes (WE). With the use of X-ray and IR-spectral analysis it was showed that the structure of PAn’s films on the surface of the Al-electrode and the Al87Ni8(REM)5 electrodes is amorphous–crystalline. At this, the PAn deposited on Al87Ni8(REM)5 electrodes has a higher degree of crystallinity. An analysis of the images of scanning electron microscopy (SEM) showed that on the surface of the WEs of amorphous alloys Al87Ni8(REM)5 the PAn’s films have spongy and porous branched morphology. An analysis of spectra of energy variance of electrons confirmed the presence on the surface of the electrodes of PAn, and showed the presence of impurities in the polymeric film of metal sulfates, which are part of the WEs.