Hot carrier distributions generated by the absorption of high-energy photons typically thermalize rapidly via various phonon-mediated relaxation processes. In this submission, it will be shown that type-II band structures allow the possibility to manipulate this non-equilibrium carrier distribution, independent of the phononic dispersion of the constituent materials. Moreover, it will be shown that the reduced overlap between electron and hole wave functions in type-II quantum wells (QWs) plays a critical role in hot carrier thermalization in these systems. Current-voltage characteristics of a multiple-QW p-i-n structure demonstrate enhanced hot carrier photocurrent extraction with increasing optical excitation power. Specifically, the elevated thermal energy of the carrier distribution induced by increase excitation power results in the tunneling of hot electrons from the QW and increased photo carrier collection.