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Optical properties of highly strained GaInAs/GaAs quantum wells (QWs) grown by molecular beam epitaxy with Sb assistance are investigated. The samples grown by Sb incorporation and Sb pre-deposition methodsdisplay high room-temperature photoluminescence (PL) intensity at extended long wavelength. This result is explained by the surfactant effects of Sb during the growth of GaInAs/GaAs QW systems. An abnormal S shaped temperature dependence of the PL peak position is found in the In0.42 Ga0.58As/GaAs triple QWs sample grown with Sb pre-deposition. By investigating the transmission electron microscope images and time-resolved PL spectra, it is found that the S-shaped temperature dependence of the PL peak position originates from the exciton localization effect brought by the Sb-rich clusters on the QW interface.