The mechanisms by which polycyclic aromatic hydrocarbons (PAHs) photodegrade in dilute (≤25 nM) aqueous solutions under varying O2 concentrations were examined. Employing previously measured photodegradation quantum yields (acquired in the absence and presence of electron donors to the PAH cation radicals, P+), excited singlet state (1P*) lifetimes, 1P*/O2 quenching rate constants and other parameters from the literature, a kinetic model was developed to analyze the fraction of PAH photodegradation that proceeds via the 1P* or excited triplet state (3P*), as well as to determine the relative contribution of electron transfer to O2 versus the direct reaction with O2 from each state. The analysis supports the following conclusions: 1) 1P* is more reactive with O2 than 3P*; 2) reaction via 1P* proceeds predominantly through electron transfer to produce the P+ intermediate, whereas reaction via 3P* proceeds primarily through direct reaction with O2 within the collision complex, consistent with the thermodynamic driving forces for electron transfer from these states; 3) although 3P* is involved significantly in the degradation of many PAHs, such as anthracene, 9-methylanthracene, acenaphthene, and perylene, it is not involved in the degradation of others such as pyrene and benzo[a]pyrene. Under aerobic conditions, photodegradation is likely to be controlled largely by 1P* lifetime and reactivity.