Structural and optical characterization of InP grown on Si(111) by metalorganic vapor phase epitaxy using thermal cycle growth X-ray diffraction has been used to characterize the heteroepitaxial growth of indium formed at the interfaces between ZnO thin film and InP monocrystalline substrates. The In formation was induced by a thermal degradation of InP during annealing in the range of 400-700°C for 3 min. The results prove that the evolution of the degradation is controlled by the decomposition of close-packed InP͕111͖ planes, while the polar character of these planes plays a very important role. Moreover, for all four employed orientations of InP substrates ͓namely ͑111͒A, ͑111͒B, ͑110͒ and ͑100͔͒, In is found to grow ͑101͒ on InP͕111͖ planes. On an InP͕111͖ interface plane, In crystallites can occur in six possible orientations characterized by a condition In͗100͘ ʈ InP͗110͘. To estimate a mismatch of the heteroepitaxy, a geometrical model of the atomic arrangement at In͑101͒-InP͑111͒ interface is given.