Photoluminescence (PL) properties of two different InGaN/GaN multiple quantum well (MQW) structures, without and with an InGaN/GaN quasi-superlattice (QSL) underlying buffer layer, were investigated. The results show that inserting a QSL between the n-GaN and MQWs can release the strain in the MQW region, since the sample with a QSL shows a smaller excitation power-dependent blue-shift of its peak energy than that without. Meanwhile, inserting a QSL enhances the localization effect of the carriers inferred from an unusual red-shift of the peak energy with increasing excitation power in low excitation range, and from a more obvious “S-shaped” temperature-dependent behavior of the peak energy characteristic: the strain release facilitates the slight composition fluctuation or phase separation of the InGaN well layers. The reduction of the quantum-confined Stark effect and enhancement of the localization effect of the MQWs induced by the strain release, greatly enhance the radiative recombination rate of the MQWs.