Glass ceramics with GdVO4: Tb nanocrystals impregnated in the highly transparent silica glass were prepared by the porous glass and sintering process and confirmed by XRD, Raman spectrum, and TEM. Spectral analysis shows that there are multifarious energy transfer processes in GdVO4: Tb nanocrystals, such as VO43− → Tb3+, Gd3+ → VO43−, Gd3+ → VO43− → Tb3+, and Gd3+ → Tb3+, and the main one is VO43− → Tb3+. In this process, 3T1,2 → 1A1 transition of VO43− transfers the energy to Tb3+ and generates 5D3 → 7F6,5,4,3,2 and 5D4 → 7F5 transitions of Tb3+. The energy transfer efficiency is 29.5%, and the excitation wavelength range of Tb3+ ions can be shifted from 230–260 nm to 280–365 nm. This shows that GdVO4 can effectively change the excitation wavelength of Tb3+, which is conducive to the application of Tb3+ ions excited by LED light sources.
