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We have investigated the thermal stability and interdiffusion of In0.53Ga0.47As/InP surface quantum wells. In these structures the optically active InGaAs layer is bounded on one side by vacuum and on the other side by InP. We obtain well‐defined photoluminescence emission spectra with high intensity. After rapid thermal annealing at temperatures between 500 and 900 °C (annealing time 1 min) we observe strong emission energy shifts of up to 316 meV. By using a simple model of ion intermixing we estimate large interdiffusion coefficients (e.g., 1.7×10−14 cm2 s−1 for T=900 °C) and an activation energy of 1.3 eV for the surface quantum wells.