The neutral donor‐bound light‐hole free exciton has been observed in AlxGa1−xAs‐GaAs multi‐quantum wells (MQWs). The transition was observed using selective excitation photoluminescence spectroscopy on two nominally 350‐A˚‐wide AlxGa1−xAs‐GaAs MQW structures in the energy region between the light‐hole and heavy‐hole free‐exciton transitions, where no other intrinsic transitions exist. The neutral donor‐bound heavy‐hole free‐exciton transition was also observed in both MQW structures. A third 150‐A˚‐wide MQW structure which showed no evidence of a donor‐bound heavy‐hole free exciton also showed no evidence of a donor‐bound light‐hole free exciton.