Dual-phases glass ceramics (GCs) containing LiYF4: Ln3+(Ln=Eu, Tb, Dy) and ZnAl2O4: Cr3+ nanocrystals (NCs) were fabricated by a conventional melt-quenching method. The structural and spectrographic characterizations indicate that Ln3+ can be doped into LiYF4 lattice and Cr3+ can be introduced into ZnAl2O4 lattice, respectively. In this regard, the luminescent centers are physically separated through a spatial isolation strategy, getting rid of adverse energy transfer processes. The dual-modal luminescence of Ln3+ and Cr3+ can be thus attained simultaneously. Also, optical thermometry based on the fluorescence intensity ratio (FIR) of Ln3+/Cr3+ is performed. Under irradiation upon 377 nm, the FIR value for Tb3+: 5D4→7F5 and Cr3+: 2E→4A2 transitions varies acutely, with a maximal relative sensitivity of 0.80%·K-1 at 570 K. The FIR-based optical thermometry for Dy3+: 4F9/2→6H13/2 and Cr3+: 2E→4A2 transitions is carried out, with a maximal relative sensitivity of 0.86%·K-1 at 573 K. As a consequence, the dual-phases GCs can be an ideal medium for the spatial isolation of luminescent centers, suppressing an adverse energy transfer process and realizing an efficient dual-mode luminescence. This is beneficial to the application of FIR-based optical thermometry for GC materials.