In this study, molecular beam epitaxial-grown GaAs/GaBiAs single quantum well systems with two different Bi contents were investigated. Spectral dependence of room temperature photomodulated reflectance (PR) and photoluminescence (PL) measurements in the temperature range of 35-300 K were employed. PR spectra indicate that increasing Bi concentration promotes a tendency to approach quantized higher energy levels in the heavy and light holes' bands due to the different effects of compressive strain, which depends on Bi concentrations. In addition, a defect level is identified at 0.71 eV at room temperature PR spectra and is attributed to a As-Ga antisite defect in GaAs barrier layers caused by the low temperature growth process. From the analysis of the temperature dependence of emission energy and amplitude in the PL spectra, localized states are determined in the range of 8 to 45 meV and attributed to the different bonding configuration of Bi clusters. Low temperature PL results imply that Bi cluster states tend to move into the valance band when Bi content increases from 2.4 to 7.0% in the GaBiAs system.