A model is proposed for a novel surface‐to‐surface segregation process which would be observed during growth by vapor deposition of thin polycrystalline films of alloys exhibiting classic surface segregation. The model depends on sufficient surface mobility to allow equilibration between surfaces of different grains and insufficient bulk mobility to allow equilibration between the surface and bulk of each grain before the present surfaces are covered by the next layer of material. This high ratio of surface to bulk mobility is easily found under standard deposition conditions. The model leads to an inhomogeneous film in which the composition of each grain is dependent on its crystallographic orientation.