We report temperature-dependent time-integrated and time-resolved photoluminescence (PL) studies of InGaN/GaN multiple quantum wells (MQWs) grown by metalorganic chemical vapor deposition. We observed anomalous emission behavior, specifically an S-shaped (decrease–increase–decrease) temperature dependence of the peak energy (Ep) for InGaN-related PL with increasing temperature: Ep redshifts in the temperature range of 10–70 K, blueshifts for 70–150 K, and redshifts again for 150–300 K with increasing temperature. In addition, when Ep redshifts, the spectral width is observed to narrow, while when Ep blueshifts, it broadens. From a study of the integrated PL intensity as a function of temperature, it is found that thermionic emission of photocarriers out of local potential minima into higher energy states within the wells is the dominant mechanism leading to the thermal quenching of the InGaN-related PL. We demonstrate that the temperature-induced S-shaped PL shift is caused by a change in the carrier dynamics with increasing temperature due to inhomogeneity and carrier localization in the InGaN/GaN MQWs. © 1998 American Institute of Physics.