The recent availability of experimental data on the hot‐electron transfer in GaSb has stimulated the present theoretical work. In the past, the only comparison between hot‐electron transport theory and experiment has been through the velocity‐field characteristic or galvanic‐magnetic phenomena. Because of the insensitivities of these macroscopic characteristics to the value of the deformation potential for nonequivalent intervalley scattering, an exact value for the latter, which governs the electron transfer between central and satellite valleys, could not be obtained. A Monte Carlo calculation has been used to obtain the deformation potential for nonequivalent intervalley scattering by interpreting the experimental data on hot‐electron transfer in GaSb obtained using the Faraday rotation.