Hot carrier photocurrent generation in a selectively contacted semiconductor quantum well is simulated using a quantum transport approach including the effects of electron–photon, electron–phonon, and electron–electron interaction. Consideration of electron–electron scattering on equal footing with photogeneration and phonon-mediated carrier relaxation is achieved via the implementation of a GW self-energy in the non-equilibrium Green’s function formalism. Spectral resolution of carrier density, scattering rates and current flow reveals the microscopic mechanism responsible for hot carrier generation and extraction in quantum wells. The existence of a hot carrier population in the system subject to carrier–carrier scattering is verified via evaluation of luminescence spectra as obtained consistently within the same formalism. This development thus represents a major advancement towards a comprehensive microscopic theory of hot carrier solar cell operation in nanostructure device architectures.