GaP and GaP/GaAsP epitaxial layers have been grown on Si substrates by metal-organic chemical vapor deposition (MOCVD). These layers were characterized by SEM and TEM plan-view and cross-sectional examination. At growth temperatures ranging from 600° C to 800° C, the initial stages of growth were dominated by three-dimensional nucleation. TEM studies showed that at high temperatures the nuclei were generally misoriented with respect to each other yielding, upon coalescence, polycrystalline layers. The growth of single-crystal layers was achieved by nucleating a 30–50 nm layer of GaP at 500° C, followed by annealing and continued growth at 750 ° C. The defect density in these structures was investigated as a function of various growth parameters and substrate conditions. A high density of structural defects was generated at the Si/GaP interface. The use of 2° off (100) Si substrates resulted in GaP layers free of antiphase domains. These results and their implications are discussed.