We studied the polarization-dependent photoluminescence (PL) of a-plane GaN /AlGaN multiple quantum wells (MQWs) grown on r-plane sapphire substrate with the various well width from 1.5 to 7.33 nm. To clarify the reasons of light emission polarization properties, we applied the 6×6 k‧p model to simulate the E-k dispersion relation and the wave functions to obtain the polarization optical transitions. According to the experimental result, the PL emission peak position exhibits a red-shifted with increasing well width, due to the reduction of the quantum confinement effect. The polarization ratio of a-plane GaN/AlGaN MQWs increased from 0.236 to 0.274 with increasing the quantum well width. This phenomenon is believed to be that y-polarized light emission gradually dominates the PL spectrum and thus enhances the polarization ratio.