Heteroepitaxial InP layers were grown by metalorganic chemical vapor deposition on novel GaAs buffer layers on Si substrates. The GaAs buffers were prepared by molecular beam epitaxy and show a reduced threading dislocation density achieved by inserting one nanometer thick Si interlayers. The structural and optoelectronic properties of the heteroepitaxial InP layers, which were investigated by transmission electron microscopy, x‐ray diffraction, and photoluminescence spectroscopy, show improvements attributed to the optimized GaAs buffer layers.