The use of heteroepitaxial structures with marker layers in conjunction with infrared reflectance spectroscopy is shown to provide a useful method for investigating the etching of compound semiconductors. The method is used with an InGaAs marker layer to investigate the vapor phase etching of InP in HCl in a typical environment encountered in a chloride vapor phase epitaxy reactor. The results are in agreement with simulations based on thermodynamic equilibrium between the solid and the gas phases and are consistent with mass transfer control of the etching process.