We report on low‐temperature photoluminescence from an ultrapure GaAs‐Al0.33Ga0.67As heterostructure grown with molecular beam epitaxy. A luminescence band centered at 1.509–1.510 eV is observed. In spectral shape and polarization this band distinguishes itself from the defect related lines of H. Kuenzel and K. Ploog [Appl. Phys. Lett.37, 416 (1980)]. Furthermore, this band disappears when the top cladding Al0.33Ga0.67As layer is removed. The emission band is further characterized by measuring its dependence on excitation density and temperature as well as its temporal behavior. We discuss possible recombination mechanisms for this band. The most likely candidate is luminescence related to a defect pair situated at or near the interface of the heterojunction.