In this study, the mixtures of ZnO and Ga2O3 powder with addition of LiCl flux were fired, the raw material mixing ratio, doping with Mn2+ and firing atmosphere effects on phosphor characteristics were investigated. When fired at 1200 °C, its phosphor powder emits a broad-band spectrum range between 375 nm to 700 nm, with a peak at 470 nm. The optimal composition of phosphors is about ZnO/Ga2O5=47/53. Manganese-doped ZnGa2O4, fired in air, exhibits two new emission bands with peaks at 506 nm (Mn2+ emission centre) and 666 nm (Mn4+ emission centre). However, if fired under vacuum, the emission spectrum presents only the 506 nm peak with increased intensity. The 666 nm emission peak derived from a little Mn2 oxidized to Mn4+ which substituted Ga3+ to occupy the B sites of the spinel structure. The emission intensity of the 506 nm peak of Zn1-xMnxGa2O4 is strongest when [Mn2+] x=0.006 and decreases markedly as the concentration of Mn2+ exceeds x=0.01. Most of the substitutional Mn2+ doping species in spinel ZnGa2O4 occupy the zinc sites. The luminescent band was associated to the spin-forbidden transition, 4T1(4G)→6A1 (6S). © 1998 Kluwer Academic Publishers