The mean-free-paths for inelastic scattering of high-energy electrons (200 keV) for AlAs and GaAs have been determined based on a comparison of thicknesses as measured by electron holography and convergent-beam electron diffraction. The measured values are 77 ± 4 nm and 67 ± 4 nm for AlAs and GaAs, respectively. Using these values, the mean inner potentials of AlAs and GaAs were then determined, from a total of 15 separate experimental measurements, to be 12.1 ± 0.7 V and 14.0 ± 0.6 V, respectively. These latter measurements show good agreement with recent theoretical calculations within experimental error.