Using a conventional reflection high-energy electron diffraction gun together with an electron energy loss spectrometer, we have combined in situ measurements of inelastic scattering intensities from Si L2,3 and Ge L2,3 core losses with reflection electron diffraction data in order to analyze the initial stages of Ge heteroepitaxy on Si(001). Diffraction data indicate an initial layer-by-layer growth mode followed by island formation for Ge thicknesses greater than 0.8–1.1 nm. The electron energy core loss data are consistent with a simple model of grazing incidence electron scattering from the growing Ge film. Reflection electron energy loss spectroscopy is found to be highly surface sensitive, and the energy resolution and data rate are also sufficiently high to suggest that reflection electron energy loss spectroscopy may be a useful real-time, in situ surface chemical probe during growth by molecular beam epitaxy