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Anisotropic property of type-II GaAs/GaAsSb heterostructures was studied by photoluminescence (PL) and photoconductivity (PC). It was found that the PL and PC spectra exhibit a strong in-plane polarization with respect to 〈011〉 axis with polarization degrees up to 40%. We showed that the polarization does not depend on the excitation intensity as well as temperature, which excludes any extrinsic mechanisms related to the in-plane anisotropy. The observed polarized optical properties of GaAsSb/GaAs multiple quantum wells was attributed to the intrinsic property of the orientation of chemical bonds at heterointerfaces. © 2002 American Institute of Physics.