The quantum yield of formation of guanine (Gua), one of the major products formed in the 254 nm steady-state photolysis of the following Gua derivatives (9-ethylguanine [9Et-Gua], deoxyguanosine [dGuo], guanosine [Guo], guanosine 5′-monophosphate [GMP]) was determined under different conditions. The formation yield increases in the following order: 9Et-Gua < dGuo ≈ Guo < GMP. Electron scavengers or triplet quenchers were incorporated into the irradiated solutions with the purpose of reacting specifically with postulated or previously identified intermediates in the photolysis of Gua derivatives. A decrease in the yield of formation of Gua is observed with increasing electron scavenger concentration or with pH. These results suggest a major contribution from Gua-derivative electron adducts on the process of N(9)–R bond breakage. At an acidic pH a tautomer of the radical cation (E) of Guo is proposed as the precursor for Gua formation. The relative efficiency of the radical cation for initiating the release of free Gua depends on the pH of the solution, being less than 39% in neutral pH. Reactions from OH radicals may also result in base release as shown using N₂O as additive. Finally, the formation of aggregates by the bases at concentrations used, plays an important role in the deactivation of the excited states and also in the probability of formation of the free base.