A theory is presented for the description of the hot electron-electron scattering at the surface of binary alloys with substitutional disorder. In particular, we consider the case were a fast electron with well-defined wave vector scatters from an electron bound to the alloy ejecting it into a vacuum state. The influence of disorder on the bound and the emitted hot electrons' states are treated using the Korringa-Kohn-Rostoker coherent potential approximation and the virtual crystal approximation. Numerical results for several metallic binary alloys are presented and analyzed revealing the interplay between disorder effects and the scattering dynamics. On the basis of the model presented in this work conclusions are drawn on the potential of using the elctron-pair-excitation as a spectroscopic tool for study of random alloys.