Oxygenated polycyclic aromatic hydrocarbons (OPAH) have received increasing attention due to their toxic effect on human health. This study comprehensively investigates the evolution of OPAH chemistry at flame temperatures. Jet-stirred reactor (JSR) experiments with benzene/phenol/C2H2/N-2 and benzene/C2H2/O-2/N-2 revealed that OPAH with oxygenated heterocycle can be formed by the addition of C2H2 at 1400K. To further clarify the evolution of OPAH chemistry in soot systems, OPAH formation and decomposition reaction pathways and kinetic parameters have been theoretically investigated. The potential energy surfaces of 1-naphtholate and 2-naphtholate growth, and thermal decomposition reactions, were calculated by combining the density functional theory B3LYP/6-311+G(d,p) and CCSD(T)/cc-pvdz methods. The reaction rate coefficients in the temperature range of 800-2500K and pressure range of 0.1-100 atm were calculated using RRKM theory by solving the master equations. The potential energy surface of C2H2+1-naphtholate and C2H2+2-naphtholate growth reactions showed that the O atom could be locked in a naphthofuran molecule with the formation of a C-O-C oxygenated heterocycle; and the reaction rates were determined by adding the C2H2 elementary step with the energy barrier of 26.0 and 19.9 kcal/mol, respectively. Thermal decomposition reactions of 1-naphtholate and 2-naphtholate yielded an indenyl radical and CO. The thermal decomposition reaction rates were significantly sensitive to the zig-zag site structure next to the C=O bond. The decomposition rate of 1-naphtholate at 1500K, with a zig-zag site near the C=O bond, was 14.8 times lower than that of 2-naphtholate with no zig-zag site near the C=O bond. Rate comparison results indicate that the C=O functional group rapidly converts to a C-O-C functional group with the addition of C2H2. The formation, growth and thermal decomposition reactions of 1-naphtholate and 2-naphtholate were added to a detailed PAH mechanism to check the effect of OPAH reactions on PAH formation chemistry. The concentration profile of naphthalene predicted by the updated PAH mechanism was lower than current PAH mechanism predictions by 29%, indicating that the OPAH reactions had a significant effect on PAH formation chemistry, and should be included in the PAH mechanism. However, due to the relatively low concentration of OPAH compared to PAH, it is possible to ignore the correlation between OPAH and soot nucleation at flame temperatures; therefore an OPAH evolution pathway (PAH -> incipient soot -> OPAH formation on soot particle -> selective thermal decomposition of OPAH), is proposed to explain the high content of OPAH molecules (e.g., 9,10-anthraquinone, benz(a)anthracene-7,12-dione, and benzanthrone) adsorbed on the soot particle. (C) 2019 The Combustion Institute. Published by Elsevier Inc. All rights reserved.