The valence shell photoelectron spectra of uracil, 1-methyluracil and 6-methyluracil have been studied experimentally and theoretically. Synchrotron radiation has been used to record spectra at photon energies of 40 and 80eV. Photoelectron angular distributions have been determined and these provide an experimental means of distinguishing between σ- and π-type orbitals. Vertical ionization energies and spectral intensities have been evaluated using the many-body Green’s function approach, thereby enabling theoretical photoelectron spectra to be derived. The calculated spectra display a satisfactory agreement with the experimental data and this has allowed most of the photoelectron bands to be assigned. Two of the outer-valence vertical ionization energies are similar to one another and the vibrational progressions associated with these transitions overlap strongly. Vibronic interaction between these states, induced through the excitation of out-of-plane vibrational modes, may lead to nonadiabatic effects. Preliminary theoretical investigation of this interaction has been performed.