The low-intensity steady-state (254 nm), microsecond flash and nanosecond (266 nm) laser photolysis of some guanine (Gua) derivatives in aqueous solution were studied. A photodestruction yield between 10⁻³ and 10⁻² at a base concentration of 75 μM was determined for 254 nm irradiation at room temperature using high-performance liquid chromatography. This yield decreases with increasing purine concentration. For a similar concentration of the purine bases (2 ± 1) × 10⁻⁵ M, the yield increases as follows: Gua ≈ 9-ethylguanine < deoxyguanosine ≈ guanosine (Guo) < guanosine 5′-monophosphate. At concentrations higher than 2 × 10⁻⁴ M the Gua derivatives' photodestruction yield seems to converge to a limiting value of the order of 10⁻⁴. This behavior is explained in terms of self-quenching and aggregation effects which deactivate the excited states of the bases. The yields of electron photoejection have been determined in the nanosecond laser photolysis (0.083) and in the low-intensity steady-state (5.8 × 10⁻³) for Guo. Competition experiments using electron scavengers suggest that the electron adducts of the bases are one of the principal species participating in the photodestruction mechanism of these monomeric Gua. Close to 75% of the total destruction yield has contributions from initial reactions of the photojected electron at neutral pH. The quantum yield of photodestruction of Guo increases when the pH is increased as follows: 4.7 × 10⁻³ (pH 1.1), 6.5 × 10⁻³ (pH 2.9), 7.7 × 10⁻³ (pH 7.5) and 8.1 × 10⁻³ (pH 11.9). This dependence on pH and the electron scavenger experiments provide further evidence for the radical anion or its protonated form as one of the principal species involved in the photodestruction of the bases at the different pH. Under oxygen saturated conditions a 22% increase in the destruction yield is observed for Guo. However, for the dinucleotides adenylyl (3′ → 5′)-guanosine and thymidylyl (3′ → 5′)2′-deoxyguanosine, the participation of the electron is 41 and 36%, respectively, suggesting that going into a more DNA or RNA-like structure, the participation of the electron adducts species in the photodamage of DNA and RNA decreases. A mechanism of photodestruction for the Gua derivatives is proposed which takes into account these findings.