In this paper we demonstrate that the improvement in the emission intensity afforded by the introduction of multiquantum barrier (MQB) structures in an InGaN/GaN multiple-quantum-well (MQW) light-emitting diode (LED) is attributable to increased excitation cross sections. Over the temperature range from 300 to 20 K, the excitation cross sections of the MQW emissions possessing MQB structures were between 9.6×10-12 and 5.3×10-15 cm2, while those possessing GaN barriers were between 8.1×10-12 and 4.5×10-15 cm2. We found, however, that the figure of merit for the LED light output was the capture fraction of the cross section; we observed that the dependence of the optical intensity on the temperature coincided with the evolution of the capture fraction. This analysis permitted us to assign the capture cross-section ratios at room temperature for the MQWs with MQBs and with GaN barriers as 0.46 and 0.35. Furthermore, the MQW system possessing well-designed MQB structures not only exhibited the thermally insensitive luminescence but also inhibited energetic carrier overflow.