Photoluminescence spectra of Mg‐doped GaAs grown by molecular beam epitaxy (MBE) are for the first time reported. Mg was introduced during MBE growth by using a synergic reaction of Mg3As2. Two near‐band‐edge emissions,gand [g‐g], were observed below bound exciton emissions which were originally obtained in Mg+ion‐implanted GaAs. It is explicitly demonstrated that there is no essential difference of photoluminescence spectra between Mg+ion‐implanted GaAs and the present material. These results conclusively indicate that the above two emissions are definitively related with the acceptor levels and exclusively not associated with crystalline defects produced by ion implantation. It is additionally presented that [g‐g] is principally established also in Mg‐doped GaAs prepared by liquid phase epitaxy, where [g‐g] is significantly suppressed due to the unintentional incorporation of Si donor atoms. For moderately Mg‐doped GaAs prepared by MBE a new fine emission with a doublet structure, temporarily denoted byAX, is obtained 5 meV below (A0, X) a bound exciton emission at neutral acceptors.