Yb3+/Er3+ ions codoped bulk glass ceramics (GC) with embedded monoclinic K3LuF6 nanocrystals are reported for potential temperature‐sensing application by using the fluorescence intensity ratio method. Such GC with good transparency and enhanced up‐conversion were prepared by the simple conversional melt‐quenching method and subsequent annealing process. Optical, structural, and temperature‐sensing up‐conversion properties were characterized systematically. Optical spectroscopy analysis confirms the incorporation of Yb3+/Er3+ into the K3LuF6 crystalline lattice, resulting in enhanced up‐conversion luminescence. Compared to other Er3+‐doped typical systems, Er3+ ions in K3LuF6 GC present large energy gap (870 cm−1) and high relative sensitivity (37.6 × 10−4 K−1 at 625 K), revealing that K3LuF6:Yb3+/Er3+ GC can be excellent candidates for optical thermometers.