Accurate understanding and measurement of the energy transfer mechanisms during thermal nonequilibrium between electrons and the surrounding material systems is critical for a wide array of applications. With device dimensions decreasing to sizes on the order of the thermal penetration depth, the equilibration of the electrons could be effected by boundary effects in addition to electron-phonon coupling. In this study, the rate of electron equilibration in 20 nm thick Au films is measured with the Transient ThermoReflectance (TTR) technique. At very large incident laser fluences which result in very high electron temperatures, the electron-phorion coupling factors determined from TTR measurements deduced using traditional models are almost an order of magnitude greater than predicted from theory. By taking excess electron energy loss via electron-substrate transport into account with a proposed three temperature model, TTR electron-phonon coupling factor measurements are more in line with theory, indicating that in highly nonequilibrium situations, the high temperature electron system looses substantial energy to the substrate in addition to that transferred to the film lattice through coupling. (C) 2007 Elsevier B.V. All rights reserved.