The invention provides terbium-doped calcium fluoride nanoparticles, a sol-gel hybrid material and a preparation method. The preparation method comprises the following steps: S1, preparing a bonded ligand; S2, heating and mixing the bonded ligand, soluble Ca salt and soluble Tb salt in ethylene glycol, then adding a fluorine source solution, and continuing heating reaction to obtain terbium-doped calcium fluoride nanoparticles; S3, dissolving the terbium-doped calcium fluoride nanoparticles in DMF, and obtaining a solution A; dissolving tetraethoxysilane in an ethanol water solution to obtain a solution B; S4, adding the solution A into the solution B, adjusting the pH value to 2-3, adding an alkaline condensation catalyst, carrying out a catalytic condensation reaction, reducing the pH value, and carrying out an aging reaction at 40 DEG C to obtain the sol-gel hybrid material. Rare earth doped nanoparticles are grafted to a skeleton of a sol-gel matrix through relatively strong interaction covalent bonds, so that doping on a molecular level is realized, and the defects of non-uniform doping and phase separation are overcome.