Absorption and fluorescence spectra of Mn2+ in phosphate, fluoro-phosphate and fluoride glasses have been studied. Combining with the result of the ESR experiment, the coordination state of Mn2+ is discussed. It can be considered that in the three kinds of glass Mn2+ ions are situated in octahedral symmetry. Theoretical calculation com forms to the experiments. In order of phosphate - fluorophosphate - fluoride glasses, the ionic contribution of the chemical bond between the transition ions and ligands iincreases gradually with the replacement of Oa~ by F—, and the site tends to more regular octahedral symmetry. The red fluorescence has been observed in all the three kinds of glass. Tii? fluorescence peak position shifts to shorter wavelength by changing the glass from phosphate to fluoride. Iron exists in fluoropliospiiate glass as Fes+ and and its absorption spectrum has been studied as well. Combining also with the ESR experiment, we consider iV+ ions axe located in octahedral symmetry.