We present photoreflectance (PR) and surface photovoltage spectroscopy (SPS) studies of GaAs1-xSbx/GaAs multiple quantum well structures with fundamental transition close to 1.3 μm. These two optical diagnostic tools are powerful supplementary techniques in the investigations of complicated quantum systems. PR gives detailed information about the heavy-holes related transitions, while SPS contains additional information concerning light-holes related ones. The comparison of experimental data and theoretical analysis based on the envelope function approximation, including strain and exciton binding energy, allows us to identify the observed PR and SPS features. The results point to the existence of weak type-I band alignment in samples being studied, and the Sb content dependent of conduction band offset is found to agree well with that reported by Wang etal [Phys. Rev. B 70, 195339 (2004)].