Reference adducts formed by reaction of deoxyribonucleosides with the ultimate carcinogenic forms of benzo[a]pyrene (BP), BP radical cation and BP diol epoxide, are essential for identifying the structures of adducts formed in biological systems. Electrochemical oxidation of BP in the presence of dG or dA produces adducts from BP radical cation. When 8 equiv of charge are consumed, four adducts are formed with dG: 7-(BP-6-yl)Gua, 8-(BP-6-yl)Gua, N2-(BP-6-yl)dG and 3-(BP-6-yl)dG. With 2 equiv of charge, however, only 7-(BP-6-yl)Gua and 8-(BP-6-yl)dG (BP-6-C8dG) are formed. Anodic oxidation of BP-6-C8dG affords 8-(BP-6-yl)Gua. Anodic oxidation of BP in the presence of dA produces 7-(BP-6-yl)Ade. Reaction of BP diol epoxide with dG yields 10-(guanin-7-yl)-7,8,9-trihydroxy-7,8,9,10-tetrahydroBP, whereas reaction with dA affords three adducts, 10-(adenin-7-yl)-7,8,9-trihydroxy-7,8,9,10-tetrahydroBP and two isomers of 10-(deoxyadenosin-N6-yl)-7,8,9-trihydroxy-7,8,9,10-tetrahydroBP . On the basis of comparative kinetic studies among adducts of aromatic hydrocarbons and dG or G, only BP-6-C8dG easily loses the sugar moiety, providing a basis for a mechanism of hydrolysis of the glycosidic bond.