The role of the relative surface kinetics of Ga and Al in determining the nature of normal and inverted interfaces defining GaAs/Al0.3Ga0.7As thin single quantum well (SQW) structures is examined via photoluminescence and excitation spectra studies on SQW structures grown under conditions determined by reflection high‐energy electron diffraction intensity dynamics to shed specific light on this issue. Results are found to be in conformity with the role of surface kinetics exemplified by computer simulations of growth and underscore the critical importance of controlling both the structural and chemical nature of interfaces via choice of optimized growth conditions.