The four diones derived from benzo[a]pyrene oxidation have been characterized by high-field nuclear magnetic resonance techniques including 2-D COSY and selective nuclear Overhauser enhancement. All the proton chemical shifts for these four quinones have been uneqivocally assigned. The direct photoxidation of benzo[a]pyrene gives a product distribution very similar to the TPP photosensitized oxygenation, suggesting singlet oxygen is involved in the former. A major product, which was characterized as the 6-seco derivative 6 and not previously reported, was detected in the singlet oxygen reaction. The presence of this product suggests a possible mechanism for quinone formation in the singlet oxygen reaction. One-electron oxidations of benzo[a]pyrene were carried out using tris(p-bromophenyl)aminium hexachloroantimonate and quenching of the radical cation with superoxide or water. The product distribution in this case was quite different from that obtained in the direct photooxidation.