Luminescent characteristics of zinc-phosphate glass and alumino-phosphate glass doped with Mn 2 + are systematically studied by means of fluorescence spectra, IR and ESR spectra. The results indicate that the emission spectra excited in the UV range are situated in the visible region and have a broad band width, and the main peak in the vibration of chemical bonds in the glass network can hardly be changed by exchanging the network modified ion. The relative intensity of Mn 2 + emission transition, 4 T 1 (G)-> 6 A 1 (S), regularly decreases and the broad emission peak shifts to the longer wavelength as the field strength of alkali and alkali earth metal ions gradually decreases. The single emission transition, 4 T 1 (G) -> 6 A 1 (S), from higher excited level (such as 4 A 1 , 4 E (G)etc.) to the 4 T 1 (G) level, is explained in views of multiphono relaxation and the variation of the local ligand field of Mn 2 + ions induced by the modifier ions is discussed. Further, the influence of alkali and alkali earth metal ions on the Mn 2 + luminescent behavior is analysed.