The structural and optical properties of InGaN/GaN multiple quantum wells (MQWs) with different barrier thick-nesses are studied by means of high resolution X-ray diffraction (HRXRD), a cross-sectional transmission electron mi-croscope (TEM), and temperature-dependent photoluminescence (PL) measurements. HRXRD and cross-sectional TEM measurements show that the interfaces between wells and barriers are abrupt and the entire MQW region has good periodic- ity for all three samples. As the barrier thickness is increased, the temperature of the turning point from blueshift to redshift of the S-shaped temperature-dependent PL peak energy increases monotonously, which indicates that the localization po- tentials due to In-rich clusters is deeper. From the Arrhenius plot of the normalized integrated PL intensity, it is found that there are two kinds of nonradiative recombination processes accounting for the thermal quenching of photoluminescence, and the corresponding activation energy (or the localization potential) increases with the increase of the barrier thickness. The dependence on barrier thickness is attributed to the redistribution of In-rich clusters during the growth of barrier layers, i.e., clusters with lower In contents aggregate into clusters with higher In contents.