Direct sampling and GC/MS analysis of fuel-rich, laminar, premixed flames of methane indicates the production of higher in-flame peak concentrations of benzene and polycyclic aromatic hydrocarbons (PAH) than in the flames of ethane under similar combustion conditions. These findings are surprising and significant because the methane flame not only had a higher H/C ratio and lower carbon density, but also produced less acetylene and soot than the ethane flame. These results suggest the significance of species containing an odd number of carbon atoms in PAH formation processes in the methane flame, as well as the importance of soot surface reactions. Although aromatic and polyaromatic intermediates constitute trace by-products of combustion, their formation is of practical concern due to their potential adverse health effects.