The effect of annealing one monolayer of Sb onp‐InP on the surface Fermi level position and the band bending due to Ag deposition on these well‐ordered surfaces have been studied using photoemission spectroscopy. The adsorption of one monolayer of Sb onp‐InP gives a Fermi level position 0.85 eV above the valence band maximum (VBM). However, with increasing annealing temperature, the band bending decreases and recovers to nearly the flatband condition above 200 °C. The Fermi level movement of annealed InP shows a correlation with the surface stoichiometry of phosphorus and indium. Ag deposition on these annealed Sb/p‐InP interfaces gives an anomalously low band bending of 0.5 eV above the VBM.