We present a spectroscopic method which utilizes virtual photons to selectively measure the electronic structure of the topmost atomic layer. These virtual photons are created when incident positrons transition from vacuum states to bound surface states on the sample surface and can transfer sufficient energy to excite electrons into the vacuum. The short interaction range of the virtual photons restricts the penetration depth to approximately the Thomas-Fermi screening length. Measurements and analysis of the kinetic energies of the emitted electrons made on a single layer of graphene deposited on Cu and on the clean Cu substrate show that the ejected electrons originate exclusively from the topmost atomic layer. Moreover, we find that the kinetic energies of the emitted electrons reflect the density of states at the surface. These results demonstrate that this technique will be a complementary tool to existing spectroscopic techniques in determining the electronic structure of 2D materials and fragile systems due to the absence of subsurface contributions and probe-induced surface damage.