Interfacial phenomena in the W-Si systems were studied by a monoenergetic positron beam. Doppler broadening profiles of the positron annihilation were measured as a function of incident positron energy. Tungsten thin films of 100 nm in thickness were deposited on p-type, 10 »cm Cz-grown Si wafers with (100) orientation by the DC magnetron sputtering method. Specimens were annealed at various temperatures in order to form suicides. It was found that the position of the interface of both W/Si and W silicide/Si is very different from the position expected from a simple situation neglecting the effect of electric field on the diffusion of positrons. This fact arouse the utility of positrons as a test charge to probe directly the electric field gradient in the Schottky barrier.