Traditional fluorescent anti-counterfeiting materials usually display monochromatic luminescence at a fixed excitation mode, which greatly reduces the efficiency of anti-counterfeiting applications. Recently, developing a multilevel anti-counterfeiting material with tunable photoluminescence is a hot topic in the arena of advanced anti-counterfeit research. Here, spinel-structured solid solutions of ZnGa 2−x (Mg/ Ge) x O 4 :0.001Mn (x = 0−1.2) have been successfully synthesized by a high-temperature solid-state reaction. In this solid solution, Mn 2+ and Mn 4+ ions were substituted for the tetrahedral site (Zn site) and the octahedral site (Ga site), respectively, which emitted a green light at ∼505 nm with afterglow and a red light at ∼668 nm with the absence of afterglow. The Mn 2+ and Mn 4+ luminescent centers in ZnGa 2 O 4 were effectively regulated by the incorporation of Mg 2+ /Ge 4+ , which resulted in more Mg 2+ ions occupying the Zn site and thus leading to more Mn 4+ ions in the Ga site and less Mn 2+ ions in the Zn site. Therefore, doping Mg 2+ /Ge 4+ contributed to a greatly enhanced red emission for Mn 4+ ions at ∼668 nm and a weakened green emission for Mn 2+ ions at ∼505 nm. The luminescent materials prepared in this study show dynamic and multicolor changes and a higher anti-counterfeiting security, indicating that they have potential for use in advanced luminescent anti-counterfeit materials. The research results in this work provide guidance for the development of multimode luminescent materials in anti-counterfeiting applications.