The UV-induced photo-relaxation dynamics of 5-bromouracil (BrU) and 5-bromo-2′-deoxyuridine (BrUrd) in aqueous solution were investigated using femtosecond time-resolved photoelectron spectroscopy with an extreme ultraviolet (XUV) probe in a flat liquid jet. Upon excitation to the ¹ππ* state by 4.66 eV UV photons, both molecules exhibited rapid relaxation into lower-lying electronic states followed by decay to the S₀ ground state. By employing a 21.7 eV XUV probe pulse, we were able to differentiate the relaxation of the excited state population from the initially excited ¹ππ* state to an intermediate electronic state with 100 fs. Computational results identify this intermediate as the ¹πσ* excited state, accessed by a ¹ππ*/¹πσ* conical intersection, and the signal from this intermediate state disappears within ∼200 fs. In contrast to thymine, formation of neither the ¹nπ* state nor a long-lived triplet state was observed. Although the ¹πσ* state is largely repulsive, prior studies have reported a low quantum yield for dissociation, and we observe weak signals that are consistent with production of hot S₀ ground state (for BrUrd) on a time scale of 1.5–2 ps. It thus appears that solvent caging effects limit the dissociation yield in solution.