Laser photodissociation spectroscopy (3.1–5.7 eV) has been applied to iodide complexes of the non-native nucleobases, 2-thiouracil (2-TU), 4-thiouracil (4-TU) and 2,4-thiouracil (2,4-TU), to probe the excited states and intracluster electron transfer as a function of sulphur atom substitution. Photodepletion is strong for all clusters (I⁻·2-TU, I⁻·4-TU and I⁻·2,4-TU) and is dominated by electron detachment processes. For I⁻·4-TU and I⁻·2,4-TU, photodecay is accompanied by formation of the respective molecular anions, 4-TU⁻ and 2,4-TU⁻, behaviour that is not found for other nucleobases. Notably, the I⁻·2TU complex does not fragment with formation of its molecular anion. We attribute the novel formation of 4-TU⁻ and 2,4-TU⁻ to the fact that these valence anions are significantly more stable than 2-TU⁻. We observe further similar behaviour for I⁻·4-TU and I⁻·2,4-TU relating to the general profile of their photodepletion spectra, since both strongly resemble the intrinsic absorption spectra of the respective uncomplexed thiouracil molecule. This indicates that the nucleobase chromophore excitations are determining the clusters’ spectral profile. In contrast, the I⁻·2-TU photodepletion spectrum is dominated by the electron detachment profile, with the near-threshold dipole-bound excited state being the only distinct spectral feature. We discuss these observations in the context of differences in the dipole moments of the thionucleobases, and their impact on the coupling of nucleobase-centred transitions onto the electron detachment spectrum.