Oxygenated poly aromatic hydrocarbons (OPAH) are widely produced in biomass combustion. Recent studies suggest significantly higher toxicity for OPAH in comparison to PAH and soot. However, the present understanding of OPAH formation chemistry is rudimentary. Hence, fundamental knowledge on the formation pathways of OPAH is urgently required to develop predictive models for adequate emission control strategies on OPAH emission in biomass combustion. In this work, the OPAH formation from oxidation of anisole, a representative biomass surrogate, was studied in a jet stirred reactor (JSR). The reaction products were in-situ sampled by molecular beam (MB) and analyzed by time-of-flight mass spectrometry (TOF-MS) using synchrotron radiation as a photon ionization source. The unique experimental setup allows direct detection and identification of large OPAH molecules. Over 40 sum formula of OPAH species were detected and identified by experiments, and a computational thermodynamic approach was applied to deduce possible isomers of OPAH species. The thermodynamic modeling approach assumes that isomers with relatively lower Gibbs free energies are more likely to be present due to possible lower activation energies in the formation pathways. Furthermore, the formation pathways of elucidated OPAH structures are proposed by analogy to the literature based on the intermediate information. The joint study of OPAH by experiments and quantum chemistry advances the understanding of OPAH formation chemistry.