China has large reserves of fluorites, and some of them display thermoluminescence. In this study, two pieces of natural luminescent fluorite were tested by inductively coupled plasma spectrometer and fluorescence spectrometer to reveal their chemical composition and emission spectra and investigated the luminescence mechanism. The results showed that the content of REE in natural luminescent fluorite was closely related to its luminescence. The richer the REE content of the sample, the stronger its luminescence. The emission peaks of the same sample differed when it was excited by different sources. Under high temperature source the main emission peaks were in the region of short wavelength. When the sample was excited by lower temperature source, the main emission peaks were in the region of long wavelength. The emission peaks were mainly related to Pr and Tb at high temperature, and some weak peaks were possibly caused by Ho. At lower temperature, the emission peaks were mainly related to Pr and Tb, and some weak peaks resulted possibly from Sm.