Recently, unusually high Schottky barrier heights (SBHs) have been realized by our group on n-type InP and related materials by an in situ electrochemical deposition of Pt. In an attempt to understand the underlying mechanism of the SBH enhancement, this article investigates in detail the evolution process of the metal (Pt, Ni, Co, and Ag)-InP interface during the in situ electrochemical process, using current–voltage, capacitance voltage, deep level transient spectroscopy, x-ray photoelectron spectroscopy, Raman, atomic force microscope, and scanning electron microscope measurements. Pt deposition by the electrochemical process realized an oxide-free, defect-free, stress-free, and nearly pinning-free interface, whereas Pt deposition by conventional electron beam evaporation and sputtering processes as well as Ag, Ni, and Co deposition by the electrochemical process gave rise to stressed and pinned interfaces. The observed large process dependence of SBH can be explained by none of the metal induced gap state model, the unified defect model, and the effective workfunction model. It is explained here by the disorder induced gap state model.