A kinetic mechanism, previously developed and successfully applied to the prediction of the formation of benzene and aromatics in different flame conditions, was applied to assess the importance of the various benzene and aromatic formation pathways in non-premixed flames. Four sets of data were tested: the methane flame and the same flame doped with toluene, ethylbenzene, and tert-butylbenzene, as studied by Anderson and co-workers. The model predicts, with good accuracy, the growth of hydrocarbons and the formation of benzene and aromatic species. The modeling shows that in the undoped methane flame, benzene formation is controlled by propargyl radical combination. Acetylene addition to C4 radicals contributes a moderate amount, whereas toluene decomposition is insignificant. The predictions are almost unaffected by the fulvene pathway. Benzene is strongly perturbed by dopant addition to methane. Predictions agree quite well with benzene concentrations in the undoped flame and agree with the increase in benzene concentration when alkylbenzenes are added. Key reactions leading to the formation of naphthalene are the propargyl addition to benzyl radicals, and, to a lesser extent, the hydrogen-abstraction acetylene-addition mechanism. Cyclopentadienyl radical combination, which is the dominant route in premixed and partially premixed flames, is insignificant in these flame conditions. (C) 2003 The Combustion Institute. All rights reserved.