We have carried out a study of the chemical reaction of silver, indium, and aluminium layers with cleaved GaP(110) surfaces using photoemission with synchrotron radiation. Core level photoelectron spectra show that silver and indium overlayers do not cause an interface reaction with GaP(110). The deposition of Al, on the other hand, leads to an extensive exchange reaction which also proceeds at low temperature, although influenced by changes in overlayer growth morphology. Surface band bending induced by the metallic overlayers was investigated as a function of deposition forn‐ andp‐type material. In contrast to earlier findings, almost identical Schottky barrier heights for In and Ag deposition are obtained, despite the large difference in work function between these two metals. Results for Al also suggest that a small range of pinning positions is responsible for the Schottky barrier heights for junctions of these metals with GaP(110). We find that large peak shifts due to a surface photovoltage induced by the photoemission light source affect the determination of the Schottky barrier heights. This and other possible reasons for the discrepancy with earlier work are discussed.