The use of room- and low-temperature photoluminescence (PL) spectroscopy for the assessment of n-type pseudomorphic AlGaAs/InGaAs/GaAs high-electron-mobility transistor structures is reported. We describe a method to determine the InAs mole fraction x, the channel layer thickness L, and the confined two-dimensional electron gas density (ns), based on the comparison between the PL transitions and the recombination energies derived from self-consistent calculations of the subband structure. A detailed analysis of the optical transitions and their dependence on the Fermi level position and temperature is performed. It is shown that, in real devices, the high sensitivity of the recombination energies and intensities on small changes of the parameters x, L, and ns allows us to detect deviations from their nominal structural parameters within the uncertainty of the molecular beam epitaxy growth technique. The present assessment procedure has been applied to a significant number of samples, and it has been backed by independent measurements of these parameters by more sophisticated techniques such as Shubnikov–de Haas and PL excitation in standard and gated samples, and by physical techniques like transmission electron microscopy and Auger spectroscopy.