A luminescence study was made of Sn‐, Te‐, or Zn‐doped AlxGa1−xAs in the Al‐rich composition range where the bandgap transition is indirect. Several luminescent bands attributed to excitons, free‐bound carrier and donor‐acceptor recombinations have been observed. The experimental data are consistent with an ``optical'' ionization energy of Sn and Te donors in the range of 59±7 meV, and 56±5 meV for Zn acceptors. These values are expected to be similar in AlAs.