Minor structural modifications to the DNA and RNA nucleobases have a significant effect on their excited state dynamics and electronic relaxation pathways. In this study, the excited state dynamics of 7-deazaguanosine and guanosine 5’-monophosphate are investigated in aqueous solution using femtosecond broadband transient absorption spectroscopy following excitation at 267 nm. The transient absorption spectra are collected under experimental conditions that eliminate the requirement to correct the data for the formation of hydrated electrons, resulting from the two-photon ionization of the solvent. The data is fitted satisfactorily using a two-component sequential kinetic model, yielding lifetimes of 210 ± 50 fs and 1.80 ± 0.02 ps, and 682 ± 40 fs and 1.4 ± 0.03 ps, for 7-deazaguanosine and guanosine 5’-monophosphate, respectively. By analyzing the results from steady-state, time-resolved, and computational calculations, the following relaxation mechanism is proposed for 7-deazaguanosine, S2(Lb) ® S1(La) ® S0, whereas a S2(Lb) ® S1(La) ® S0(hot) ® S0 relaxation mechanism is proposed for guanosine 5’-monophosphate. Interestingly, longer lifetimes for both the Lb ® La and the La ® S0 internal conversion pathways are obtained for 7-deazaguanosine compare to guanosine 5’-monophosphate. Collectively, the results demonstrate that substitution of a single nitrogen for a methine (C-H) group at position seven of the guanine moiety stabilizes the 1pp* Lb and La states and alters the topology of their potential energy surfaces in such a way that the population dynamics of both internal conversion pathways in 7-deazaguanosine are significantly slowed down compared to those in guanosine 5’-monophosphate.