The epitaxial growth of III-V semiconductors on Si for integrated optoelectronic applications is currently of great interest. GaP, with a lattice constant close to that of Si, is an attractive buffer between Si and, for example, GaAsP. In spite of the good lattice match, the growth of device quality GaP on Si is not without difficulty. The formation of antiphase domains, the difficulty in cleaning the Si substrates prior to growth, and the poor layer morphology are some of the problems encountered. In this work, the structural perfection of GaP layers was investigated as a function of several process variables including growth rate and temperature, and Si substrate orientation. The GaP layers were grown in an atmospheric pressure metal organic chemical vapour deposition (MOCVD) system using trimethylgallium and phosphine in H2. The Si substrates orientations used were (100), 2° off (100) towards (110), (111) and (211).