Guanosine (G) derivatives in nonpolar aprotic solvents self-assemble to intricate hydrogen-bonded supramolecular architectures, including dimers, ribbons, and cyclic quartets. Considerable interest exists in the nature of the excited electronic states, their lifetimes and the radiationless deactivation mechanisms of the molecules in those environments. Here, we report on the electronic relaxation of G in the extended H-bridged networks in solution in n-hexane. The resulting architectures were sampled by FTIR, UV, and CD spectroscopies. The dynamics after 260 nm photoexcitation were investigated by femtosecond fluorescence up-conversion, broadband UV-vis absorption, and single-color deep-UV measurements. The observed temporal profiles reveal a hierarchy of relaxation processes, with lifetimes τ1 = 0.63 ± 0.03 ps, τ2 = 5.9 ± 0.3 ps, and τ3 = 62 ± 7 ps. Moreover, about 10% of the photoexcited molecules transform to much longer-lived product states with lifetime τ4 ≈ 3.6 ± 1.0 ns. These excited-state lifetimes are much longer than in the G monomer or the G·G dimers studied previously, hinting at sizable energy shifts among the excited ππ* and nπ* states and trapping of excited-state population in the supramolecular networks by potential energy barriers along the optimal electronic deactivation pathways of the molecules.