The influence of rapid thermal annealing (RTA) on the structural and luminescence properties of GaAs/AlGaAs quantum wells is investigated. The results show that, when the annealing temperature is 800 ℃, the crystal quality and photoluminescence (PL) intensity is significantly improved. When the annealing temperature is 900 ℃, the crystal quality and PL intensity decrease. According to the peak energy theory, the luminous mechanism at room temperature of PL peaks is obtained. A whole RTA-induced blue shift of PL peaks is observed by peak-differentiating and fitting. The PL mapping demonstrates that RTA can significantly improve the whole crystal quality and the luminous uniformity of materials.