We report some recent results on thick heteroepitaxial growth of GaP on GaAs substrates and on orientation-patterned (OP) GaAs templates conducted in a hot-wall horizontal quartz reactor for Hydride Vapor Phase Epitaxy. The growths on the plain substrates resulted in up to 500 mm thick GaP with smooth surface morphology (RMS <1-2 nm) and high crystalline quality (FWHM = 100-150 arcsec), comparable to the quality of the related homoepitaxial growths of GaP on GaP. Up to 300 mm thick OPGaP quasi-phase matching structures with excellent domain fidelity were also heteroepitaxially grown with high reproducibility on OPGaAs templates in support of frequency conversion laser source development for the mid and longwave infrared. We studied the GaAsxP1-x ternary transition layer that forms between the growing film and the substrate. We also undertook steps to determine some important characteristics of heteroepitaxy such as thickness of the pseudomorphous growth and periodicity of the expected misfit dislocations. The formation of these and some other defects and their distribution within the layer thickness was also investigated. Samples were characterized by Nomarski optical microscopy, transmission optical measurements, transmission electron microscopy, scanning electron microscopy, atomic force microscopy, X-ray diffraction and energy dispersive X-ray spectroscopy. The focus was predominantly on the interface and, more precisely, on what influence the pre-growth surface treatment of the substrate has on the initial and the following stages of growth, as well on the mechanisms of the strain relaxation from the lattice and thermal mismatch between layer and substrate. The efforts to accommodate the growing film to the foreign substrate by engineering an intermediate buffer layer were extended to thick growths of GaAsxP1-x ternary with the idea to combine in one material the best of the nonlinear properties of GaP and GaAs that are strictly relevant to the pursued applications. Published by Elsevier B.V.