We investigate the differences in optoelectronic performances of InGaN/AlGaN multiple-quantum-well (MQW) near-ultraviolet light-emitting diodes by using samples with different indium compositions. Various macroscopic characterizations have been performed to show that the strain-induced piezoelectric field (FPZ), the crystal quality, and the internal quantum efficiency increase with the sample’s indium composition. This improved performance is owing to the carrier recombination at relatively defect-free indium-rich localized sites, caused by the local in-plane potential-energy fluctuation in MQWs. The potential-energy fluctuation in MQWs are considered to be originating from the combined effects of the inhomogeneous distribution of point defects, FPZ, and indium compositions.