A structural analysis of the luminescence spectra of molecular‐beam‐epitaxy grown GaAs layer, in the energy range 1.5040–1.5110 eV (g‐vlines) is reported. At least two distinct recombination processes are distinguished from the selectively excited photoluminescence, not the excitation spectra and the luminescence polarization measurements. The relation of several lines in this emission band with oriented complex defects is established and suggested acting as isoelectronic centers.