Electronic structure/Rice-Ramsperger-Kassel-Marcus Master equation calculations were applied to unravel the oxidation mechanism and kinetics of the cyclopenta[a]naphthalenyl radical with molecular oxygen. The reaction has been shown to proceed through the addition of O2 in the ortho-position in the five-membered ring of C13H9. At low temperatures, the reaction yields a collisionally stabilized C13H9O2 complex, which rapidly decomposes back to the reactants. In the high-temperature regime, above 800, 900, 1125, and 1375 K at pressures of 0.03, 1, 10, and 100 atm, respectively, the reaction forms bimolecular products including 3H-/1H-cyclopenta[a]naphthalen-3-one + OH as the prevailing product together with 1-ethanol-substituted 2-naphthyl radical + CO and 3H-benzo[f]chromen-3-one + H as minor ones, with the branching ratio of the OH elimination channel growing with temperature and the rate constants for the individual bimolecular channels being independent of pressure. The calculated rate constants and product branching for cyclopenta[a]naphthalenyl + O2 closely agree with those reported earlier for the indenyl + O2 reaction and are recommended for the combustion kinetic models for the oxidation reactions of five-membered rings on free edges of larger polycyclic aromatic hydrocarbon molecules. The results also confirm that the oxidation of a π radical located on a five-membered ring with molecular oxygen is very slow.