Exciton localization in GaN/AlGaN quantum well structures is studied by photoluminescence. An anomalous temperature behavior of the photoluminescence from the quantum well is observed. With increasing temperature the energy position of the excitonic emission line first decreases up to 20 K, then increases, reaching a maximum around 90 K, and then decreases again in the higher temperature range. The observed behavior is discussed in terms of localization at the interface potential fluctuations. It is argued that the temperature activated migration and subsequent release of the excitons from traps that occurs between 20 K and 90 K are responsible for the observed S-like shape of the energy dependence. The obtained results allow a direct characterization of the energy fluctuations present in GaN/AlGaN quantum wells grown by different techniques.