Photoluminescence (PL) and surface photovoltage spectroscopy (SPS) are used to characterize a series of highly strained InxGa1−xAs/GaAs quantum well (QW) structures grown by metal organic vapor phase epitaxy with different indium compositions (0.395≤x≤0.44) in the temperature range of 20K≤T≤300K. The PL features show redshift in peak positions and broadened lineshape with increasing indium composition. The S-shaped temperature dependent PL spectra have been attributed to carrier localization effect resulting from the presence of indium clusters at QW interfaces. A lineshape fit of features in the differential surface photovoltage (SPV) spectra has been used to determine the transition energies accurately. At temperature below 100K, the light-hole (LH) related feature shows a significant phase difference as compared to that of heavy-hole (HH) related features. The phase change of the LH feature can be explained by the existence of type-II configuration for the LH valence band and the process of separation of carriers within the QWs together with possible capture by the interface defect traps. A detailed analysis of the observed phenomena enables the identification of spectral features and to evaluate the band lineup of the QWs. The results demonstrate the usefulness of PL and SPS for the contactless and nondestructive characterization of highly strained InGaAs/GaAs QW structures.