The 1.283‐eV luminescence band observed in GaAs grown from Ga‐rich melts is attributed to a donor–double‐acceptor pair transition which leaves the negatively charged final state of the double acceptor in the 2S3/2excited state. This assignment is shown to be consistent with the estimated energy of such a transition and with the results of Hall effect, infrared absorption, and luminescence measurements. It is proposed that similar emission bands should be observed for other double acceptors and that their observation provides strong evidence for the double‐acceptor nature of such impurities.