In oxyfluoride glass-ceramics, the fluoride nanocrystals doped with rare earth ions were dispersed in an oxide network. The emission of Eu3+ has high sensitivity to different crystal field and is suitable for microstructure research in neoceramic glass. Different oxyfluoride glass ceramics doped with Eu3+ were prepared. The variation of the emission spectra of Eu3+ in different glass ceramics confirms the applicability of Eu3+ ions in neoceramic glass as microprobe before and after heat treatment.