It is shown that a combination of low‐temperature photoluminescence and luminescence excitation spectroscopies together with appropriate modelization can provide the precise information needed for a thorough control of interdiffusion in quantum well structures. A fit of observed and calculated transition energies up to five energy levels, using the interdiffusion length as a unique parameter, is considered. The potentiality of this procedure to fully characterize the interdiffusion process is illustrated by considering the examples of lightly and heavily intermixed GaAs‐AlGaAs multiquantum wells.