A photoluminescence emission band at 830 nm has been detected in single heterojunction quantum well structures (modulation‐doped structures) in the range of 250–400 K. This emission band is observed neither in heterojunction structures without a two‐dimensional electron gas (2DEG), nor inn+AlGaAs and GaAs. The intensity of the emission band increases as the mobility of the samples with 2DEG and shows excitonic behavior in its variation with incident laser excitation intensity. This photoluminescence emission was observed in samples grown by both molecular beam epitaxy and by organometallic vapor phase epitaxy. This effect may be useful as a rough identification of high quality, modulation‐doped heterostructures.