Europium doped transparent glass ceramic containing orthorhombic YF3 particles was prepared. X-ray photoelectron spectroscopy, photoluminescence spectra, time-resolved decay curves confirmed the formation of Eu2+ and Eu3+ dual-emitting centers in an air atmosphere. Furthermore, it was demonstrated that Eu2+ stayed in glass matrix while Eu3+ partitioned into YF3 crystal lattice after glass crystallization. Benefited from their completely different thermal-quenching behaviors, linear temperature-dependent fluorescence intensity ratio between Eu2+ and Eu3+ was achieved, showing the advantages of high sensitivity, superior signal discriminability as well as excellent thermal stability for temperature determination.