Conductive pyrolytic carbon materials were obtained in wet impregnation process followed by controlled pyrolysis. Poly-N-vinylformamide (PNVF) as well as mixture of PNVF and pyromellitic acid (PMA) were applied as carbon precursors. Composition of carbon precursors was optimized in terms to obtain best electrical properties of pyrolytic carbons. Mixture of PNVF and PMA as well as pure PNVF were deposited on the model alumina (α-Al2O3) support to form conductive carbon layers (CCL). The optimal composition of the polymer precursors was determined by Raman spectra and electrical conductivity measurements. The carbonization conditions were optimized using complementary thermal analysis methods (EGA(FTIR)–TG/DTG/STDA). It was found that the addition of PMA to polymer precursor PNVF decreases temperature of formation of condensed graphene structures, domains of electrical conductivity, thus, the formation temperature of pyrolytic carbons with desired electrical properties may be decreased.