Dual-emitting and thermochromic manganese ion single doped ZnGa2-yAlyO4 phosphors were prepared by solid-state reaction. The regulation of the valence state and the luminescent properties, especially the luminescent thermal stability of manganese ions in ZnGa2-yAlyO4, are discussed in detail. When excited by ultraviolet (UV) light, the emission spectra of ZnGa2O4:Mn2+,Mn4+ present an ultranarrow green emission band at 503 nm with a fwhm of 22 nm, which derives from the Mn2+ ions formed by the self-reduction of doped Mn4+, and a red emission band of the Mn4+ ions at 669 nm. In addition, a ZnGa2-yAlyO4:Mn2+,Mn4+ solid solution was designed and synthesized by Al3+ replacing Ga3+. The doping of Al3+ effectively inhibited the degree of Mn4+ self-reduction to Mn2+, thus realizing the regulation of valence state of manganese ions. Interestingly, the thermal stability of luminescence shows that the response of Mn2+ and Mn4+ to temperature is obviously different in ZnGa2-yAlyO4, implying the potential of the prepared phosphors as optical thermometers. Subsequently, three kinds of optical thermometers with superior color discrimination and high relative sensitivity (S-r) based on the fluorescence intensity ratio (FIR) technique were realized in 100-475 K. The S-r value of ZGO:0.005Mn/ZGA0.5O:0.005Mn/ZGAO:0.005Mn phosphors can be as high as 4.345%/4.001%/3.488% K-1 (at 350/325/400 K), reflecting the great potential of ZnGa2O4:Mn2+,Mn4+ for optical thermometry applications.