Two ways of preparation of the conductive carbon covered grains of α–Al 2 O 3 have been successfully tested. The water suspended alumina grains were pre-covered by polymeric films obtained by precipitation polymerization of acrylonitrile or by wet impregnation from solution of poly-N-vinylformamide. The obtained precursors were converted into highly conductive composites due to conductive carbon layer (CCL) formed on surface of the pyrolysed precursors. The CCLs were characterized by Raman spectra and electrical conductivity measurements. The carbonization conditions were optimized using complementary thermal analysis methods (TGA, DTG, SDTA and MS-EGA).