Molecular beam epitaxy-grown InGaAs/GaAs multilayer structures were used to characterise for their indium composition, quantum well widths and energy levels in quantum wells employing low-temperature photoluminescence spectroscopy. The effect of surface segregation and thermal desorption of indium atoms in these structures which changes the intended square well and barrier profiles is demonstrated. These shape changes in the well and barrier must be taken into account to correctly predict the quantum well energy level positions and hence the indium composition and the quantum well width. (C) 2001 Elsevier Science Ltd. All rights reserved.