InGaP/GaAs heterointerfaces grown by metalorganic chemical vapor deposition have been characterized by a high-resolution x-ray diffraction analysis of multiple quantum well structures. The flow of AsH3to InGaP surface produces an InGaAs-like interfacial layer at the GaAs-on-InGaP interface, indicating P atoms of the InGaP surface are easily replaced by As atoms. The flow of PH3to GaAs surface, on the other hand, does not make any detectable interfacial layer, indicating that almost no As atoms of the GaAs surface are replaced by P atoms. It is also found that the flow of trimethylgallium (TMG) to the InGaP surface produces a GaP-like interfacial layer. This interfacial layer is probably formed by the reaction between TMG and excessive P atoms on the InGaP surface or residual PH3in the growth chamber. ©1997 American Institute of Physics.