In this study, the UV photodissociation of gas phase ion pairs of the ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, [emim]+[tf2n]-, is shown to proceed primarily through radical intermediates. [emim]+[tf2n]- ion pairs have been shown previously to undergo two-photon-dependent dissociation, but the mechanisms of this have not been probed in detail. By employing a two-laser pump probe spectroscopy and time-dependent density functional theory (TD-DFT) calculations, we have illustrated that one of the major UV photodissociation pathways in [emim]+[tf2n]- ion pairs is an intermolecular electron transfer wherein the anion transfers an electron to the cation resulting in two neutral open-shelled products. These products were observable for at least 1.6 μs post photodissociation, the experimental limit, via detection of the [emim]+ cation. This data demonstrates that the likely photoproducts of [emim]+[tf2n]- UV photodissociation are two neutral species that separate spatially, demonstrated through lack of observed relaxation pathways such as electron recombination. TD-DFT and frontier molecular orbital analysis calculations at the MN15/6-311++G(d,p) level are employed to aid in identifying excited state characteristics and support the interpretations of the experimental data. The energetic onset of the intermolecular electron transfer is consistent with previously observed [emim]+[tf2n]- absorption spectra in the bulk and gas phases. The similarities between bulk and gas phase UV spectra imply that this electron-transfer pathway may be a major photodissociation channel in both phases.