The magnetophotoluminescence peaks in the ‘‘two‐electron’’ satellites of the donor bound exciton transitions corresponding to the shallow donors S, Si, Ge, Sn, and Te have been identified by correlation of photoluminescence measurements with photothermal ionization measurements on the same high‐purity epitaxial GaAs samples. The magnetophotoluminescence measurements were made at 1.7 K and a magnetic field of 9.0 T. These results permit the use of magnetophotoluminescence measurements for the identification of residual donor impurity species in high‐purity GaAs.