The growth procedure of the Si/GaP( Ⅲ )heterointerface with Si electron beam evaporation in an improved ADES-400 photo-electron spectrometer is introduced in this paper. Then the status of formation and valence band discontinuities of Si/GaP(Ⅲ ) heterointerfaces that grown under different conditions are analysed or measured in situ by photoemission. The relation of the ΔEv values with the status of the interface and the shift of atomic core levels is discussed. The growth condition of the abrupt and ordered Si/GaP(Ⅲ)heterointerfaces is determined. The value of valence band discontinuity in this case is 0.80eV. It agrees with theoretical results.