In the invention, up-conversion luminescent calcium fluoride nano particles being 5-10 nm are produced through a hydrothermal method, and then a bio-glass fiber composite material doped with the up-conversion luminescent nano particles is produced through a sol-gel combined electrostatic spinning method. The method is simple and has strong operability. The fiber has controllable size, uniform distribution and good continuity. The bio-glass fiber composite material has good biocompatibility and strong bioactivity, is degradable, has wide application prospect in bio-medicines and has important applications in the fields of scaffold for tissue engineering, bioprobes, tissue or cell imaging, medicine tracing, etc.