Fluorite is rich in mineral resources and its gorgeous colors and excellent luminescence characteristics have attracted the attention of many scholars. In this paper, the composition, structure, luminescent properties, and the potential application value of three fluorites with different colors and are systematically analyzed. The results show that REE and radioactive elements have effects on the structure, color, and luminescence of fluorite. Radioactive elements Th and U will aggravate the formation of crystal defects in fluorite. The green color is related to Ce3+ and Sm2+. Colloidal calcium and F− center are responsible for the blue-purple color of fluorite. There are many luminescent centers, such as Eu, Pr, Dy, Tb, Er, and Sm, in fluorite. The blue fluorescence is mainly caused by 4f7-4f65d1 of Eu2+. In addition, it is found that fluorite has certain temperature sensing properties in the temperature range of 303–343 K.