The possibility of forming a strained pseudomorphous quantum well (QW) consisting of a InxGa1 –xAsyP1 –y quaternary alloy upon the deposition of InAs onto the surface of an epitaxial GaP/Si layer with a developed relief is demonstrated. The QW is studied by means of transmission electron microscopy and steady-state photoluminescence spectroscopy. The formation of two QW segments different in width and composition of the InxGa1 –xAsyP1 –y alloy is observed; in this case, an increase in the QW width is accompanied by a decrease in the content of In and As atoms. The lateral dimensions of the QW segments are no smaller than 20 nm. The QW segments correspond to two different low-temperature photoluminescence bands. The experimentally observed phenomena are interpreted on the assumption of transformation of the surface under the action of elastic strains during heteroepitaxy of InAs on the terraced GaP surface.