Annealing an Fe(96.5)Si(3.5) (100)/(110) bicrystal, containing 90 ppm P, leads immediately to a strong segregation of silicon. The Si atoms, however, desegregate subsequently and are displaced by P, whose segregation enthalpy is larger than that of silicon. The corresponding surface structures formed on both faces have been studied using complementary methods: Scanning tunneling microscopy (STM) to obtain atomically resolved geometrical information and Auger electron spectroscopy (AES) for the determination of the surface composition. Si substitutes surface Fe atoms on both faces and forms ordered surface alloys, whereas P occupies hollow sites on the surface. Si and P form c(2 x 2) superstructures on the (100) surface, whereby each segregated phosphorus atom blocks in the average one silicon segregation site. The (110) surface, on the other hand, is characterized by a c(1 x 3) Si superstructure. Due to the anisotropy of this surface the P/Si exchange proceeds by the formation of silicon coverage decreasing domain boundaries within the silicon structure, which are simultaneously occupied by P atoms. Furthermore the comparison of the AES and STM derived phosphorus coverages indicates a P multilayer segregation on the (110) surface.