Mn⁴⁺ activated red phosphor is one of the current research hot-spots in the field of white light emitting diodes (wLEDs). The shortest emission of Mn^{4+ 2}E→⁴A₂ transition in aluminate is 651 nm realized in MgAl₂O₄, but the doped manganese ions exists in multiple valence states (+2/+4/+3, etc.) due to the fact that there exist two cationic sites (Mg²⁺/Al³⁺) forming tetrahedron or octahedron coordination in the spinel structure. In this study, variation of the Al₂O₃ polymorphs (γ/α ratio) in the starting materials and post-annealing were used to control the doping sites and valence state of manganese ions in the MgAl₂O₄ structure. The results show that a high α/(α+γ) ratio of starting Al₂O₃ favors the formation of Mn²⁺ while a low α/(α+γ) ratio of starting Al₂O₃ favors the formation of Mn⁴⁺ dopant. By using highly active nano-γ-Al₂O₃ as the Al³⁺-bearing source, the occupancy of manganese ions in the Mg²⁺ site and the formation of Mn²⁺ valence state were effectively suppressed. Bright and pure MgAl₂O₄:Mn⁴⁺ phosphors in which only the red luminescence from Mn⁴⁺ was observed in the visible spectral region were successfully prepared via once heat treatment at 1550 ℃ for 5 h in air. The intrinsic reason for the dependence of manganese doping valence state on the Al₂O₃ polymorph lies in that the reactivity of Al₂O₃ determined the sequences of doping reactions and then the doping site/valence of manganese ions in MgAl₂O₄:Mn. All the above data demonstrated that the control of reaction sequences was a new method to regulate the valence state of manganese in aluminate phosphors.