Paths of polycyclic aromatic hydrocarbons (PAHs) formation in flames including HACA and RSFR mechanisms are shortly presented. Results of experiments carried out in a laboratory scale atmospheric-pressure premixed CH4/air flame are reported. Concentration profiles of different PAHs were recorded along the axis of the flame. Samples were obtained using stainless steel water-cooled probe and XAD-2 resin trap. Gas chromatography combined with FID detector was used to determine individual PAHs. The axial concentration profiles of selected PAHs in studied flames indicated that PAHs are formed rapidly at the beginning of the flame and their concentrations decrease downstream. The final PAHs concentrations in CH4 flames doped with toluene (aromatic structure) are higher than those in CH4 flames especially at φ >1,1 (rich mixture). Also addition of acetylene produces much higher PAHs concentrations.