Polarization-matched quantum wells (QWs) can lead to maximized electron-hole wave functions overlap and low efficiency droop at high current density. By using the modern theory of polarization with hexagonal reference, c-plane InAlN/InGaN QWs were explored and designed for polarization matching. The simulation results show that, even on c-plane, polarization-matched structures can be achieved by adjusting strain and material composition. The In composition of larger than 35% of InAlN was required to match the total polarization of InGaN at any given composition. Considering the bandgap’s bowing factors of III-nitride ternary alloys, In0~0.1Ga1.0-0.9N as quantum barrier (QB) provided enough potential barriers for In0.35~0.45Al0.65-0.55N to form a multiple QW (MQW) structure. The results indicated that improper resistance of MQW and the existing fixed charge between the interfaces of p-type region/MQW and n-type region/MQW could result in nonuniform carrier distributions and current leakage, respectively. Furthermore, we found that In0.41Al0.59N/In0.1Ga0.9N polarization-matched MQW had proper resistance; however, such structure produced a huge polarization fixed-charge between the junction interface. By studying the strain level of InAlN QW and GaN QB, which can be grown on AlN/GaN superlattice templates, the In0.33Al0.67N/GaN polarization-matched MQW structure has been specifically designed with small resistance and without inducing improper polarization fixed charge. By optimizing the number and thickness of QWs, the 425nm LED has relative IQE of 56% and efficiency droop of only 7% at high current density of 333 A/cm2. This study provides guidance for development of In-rich InAlN materials.