Photoluminescence (PL) and photoreflectance (PR) measurements have been performed to investigate the intermixing behavior of Al and Ga in GaAs/AlAs multiple quantum wells (MQWs) grown by molecular‐beam epitaxy and treated by rapid thermal annealing. These results indicate that the magnitude of the disordering for a GaAs/AlAs MQW increases as the layer thickness increases. When the GaAs/AlAs MQWs with layer thicknesses of 34 A˚ are annealed at 950 °C for 10 s, the GaAs/AlAs MQWs are totally intermixed, resulting in a formation of an Al0.45Ga0.55As alloy. For the intermixed GaAs/AlAs MQWs, PL spectra show dominantly the &Ggr;‐valley direct transition, and PR signals show that the peaks originating from the interband transitions disappear. The observed increases of the full width at half‐maximum (FWHM) in the PL spectra for the annealed GaAs/AlAs MQWs originate from the nonuniformity of the intermixing as a function of depth, and the decrease of FWHM in the PL spectra for the GaAs/AlAs MQWs annealed for longer times is due to the formation of Al0.45Ga0.55As alloys in the GaAs/AlAs MQWs. ©1995 American Institute of Physics.