We have studied the influence of indium (In) composition on the structural and optical properties of InxGa1-xN/GaN multiple quantum wells (MQWs) with In compositions of more than 25% by means of high-resolution x-ray diffraction (HRXRD), photoluminescence (PL), and transmission electron microscopy (TEM). With increasing the In composition, structural quality deterioration is observed from the broadening of the full width at half maximum of the HRXRD superlattice peak, the broad multiple emission peaks of low temperature PL, and the increase of defect density in GaN capping layers and InGaN/GaN MQWs. V-defects, dislocations, and two types of tetragonal shape defects are observed within the MQW with 33% In composition by high resolution TEM. In addition, we found that V-defects result in different growth rates of the GaN barriers according to the degree of the bending of InGaN well layers, which changes the period thickness of the superlattice and might be the source of the multiple emission peaks observed in the InxGa1-xN/GaN MQWs with high In compositions.