A -plane InExGa1-xN/GaN (x=0.09, 0.14, 0.24, and 0.3) multiple-quantum-wells (MQWs) samples, with a well width of about 4.5 nm, were achieved by utilizing r -plane sapphire substrates. Optical quality was investigated by means of photoluminescence (PL), cathodoluminescence, and time resolved PL measurements (TRPL). Two distinguishable emission peaks were examined from the low temperature PL spectra, where the high- and low-energy peaks were ascribed to quantum wells and localized states, respectively. Due to an increase in the localized energy states and absence of quantum confined Stark effect, the quantum efficiency was increased with increasing indium composition up to 24%. As the indium composition reached 30%, however, pronounced deterioration in luminescence efficiency was observed. The phenomenon could be attributed to the high defect densities in the MQWs resulted from the increased accumulation of strain between the InGaN well and GaN barrier. This argument was verified from the much shorter carrier lifetime at 15 K and smaller activation energy for In0.3Ga0.7N/GaN MQWs. In addition, the polarization-dependent PL revealed that the degree of polarization decreased with increasing indium compositions because of the enhancement of zero-dimensional nature of the localizing centers. Our detailed investigations indicate that the indium content in a -plane InGaN/GaN MQWs not only has an influence on optical performance, but is also important for further application of nitride semiconductors.