We have investigated the formation of the Schottky barrier on bulk PbTe single crystals, cleaved along the (100) surface, for several metal overlayers (Al,Au,In,Pb) by means of photoelectron spectroscopy with synchrotron radiation. We find that the Schottky barrier height varies widely with the metal used thus indicating that the Fermi level is not pinned for these interfaces. Pb and Al overlayers form a degenerate n‐type interface, while Au and In give nondegenerate interfaces. The height of the barrier follows the correlation with ΔHR, the interfacial heat of reaction, found for other semiconductors. The index of interface behavior S estimated from our data, 0.2, is in disagreement with the results obtained from other semiconductors, correlating S with the heat of formation of the semiconductor. From a morphological point of view, the interface type is in agreement with predictions based on the heat of interface reaction ΔHR. The interfaces are found to be morphologically very different, ranging from th...