This study simulates a high-temperature reaction in a plug-flow reactor (PFR) for the aromatization of methane via oxidative coupling of methane (OCM) using a state-of-the-art gas-phase chemical kinetic mechanism. Benzene is formed from a methane-oxygen (CH4-O2) feed via formation of ethylene through OCM followed by homogeneous gas-phase aromatization of C2H4 after O2 depletion. Because both OCM and C2H4 aromatization are exothermic reactions, the process is advantageous over an endothermic non-oxidative methane aromatization reaction. For the OCM reaction, the previously reported mechanism in which the catalyst achieves the quasiequilibrated formation of OH• from an H2O-O2 mixture was included in the combustion chemistry network. It was evident that OH• formation increased benzene yield as a consequence of enhanced C2H4 yield from the OCM. The influence of temperature, CH4/O2 ratio and contact time on benzene yield was elucidated, and reaction pathways leading to aromatic formation were analyzed. The maximum benzene yield on a carbon basis at a total pressure of 1 atm reached 10% at CH4/O2 ratios from 3 to 6 and temperatures of 800 to 900ºC (isothermal). Our analysis on the differential rates of production suggest that benzene is formed from the benzyl radical via toluene and from the reaction between allyl and propargyl. Adiabatic operations were found to be beneficial for reducing external heat supply (i.e., inlet temperature) by utilizing the exothermic reactions. ASSOCIATED CONTENT Supporting Information. Reaction profiles without OH• contribution Figure S1, Table S1; Water addition effects on adiabatic reactor temperature profiles Figure S2.