Since the in-depth research on the theory and technology of luminescent materials, luminescent materials have been widely used in white LED lighting, optical imaging, optical storage, optical communication, optical fiber laser, and other fields. In recent years, it has been found that the luminescent materials prepared by introducing phosphorus as co-doped elements show unique advantages in optical properties, which has become the key factor to solve the bottleneck of luminescent properties of many luminescent materials. In this paper, the preparation methods and optical properties of phosphosilicate luminescent glass was reviewed. Several mainstream preparation methods of luminescent materials and their phosphorus doping technology were introduced, as well as the spectral characteristics of various luminescent ions in the coordination environment of P⁵⁺, which shows the great advantages of phosphosilicate luminescent glass and optical fiber in the fields of optical communication and optical fiber laser. Finally, the application prospect of a variety of phosphorus doped active special optical fibers is prospected.