Mn+ ions were implanted into ultrapure GaAs layers grown by molecular beam epitaxy. 2 K photoluminescence revealed that in addition to the well‐established Mn‐related deep acceptor emission at ∼1.41 eV, four new shallow emissions denoted by (Mn°, X), ‘‘G’’, ‘‘H’’, and (D, A)2 are formed in the near band edge when the Mn concentration [Mn] exceeds 3×1016 cm−3. Both ‘‘G’’ and ‘‘H’’ exhibit no energy shift with growing [Mn] up to 1×1019 cm−3. In contrast, for shallow acceptor‐ (such as C) doped GaAs with extremely low background concentrations of donor impurities, a series of [g‐g]‐like energy levels, which present strong energy shifting with increasing acceptor concentration, are universally formed. These results show that pairs between deep Mn acceptors do not produce such [g‐g] like energy levels.