In this research, ZnO-Al2O3-SiO2 glass-ceramics were prepared with various contents of Li2O (1–5 mol.%). No nucleating agent was used. The prepared glasses were converted into glass-ceramics through nucleation and crystal growth processes. The physical parameters and crystallization behavior of the samples were assessed through differential thermal analysis (DTA), dilatometry, x-ray diffraction (XRD), field-emission scanning elec- tron microscopy (FESEM), and Fourier transform infrared spectroscopy (FTIR). The incorporation of Li2O declined the Tg level from 820 ◦C to 768 ◦C. Gahnite and eucryptite were the dominant phases in the glass- ceramics. A rise in the Li2O content to 5 mol% led to an opaque glass-ceramic. Results showed that the addi- tion of the lithium oxide led to the formation of a eucryptite phase alongside the primary gahnite phase. The dimension of the crystals was in the range of 20 nm through controlling the nucleation temperature and growth of the glass-ceramics. In order to induce photoluminescence (PL) property into the glasses, cerium oxide was added to all samples at 2 wt.%. The PL behavior was then investigated with the help of PL spectrum. TGC-Li3 sample exhibited up to 10 times higher PL intensities than the corresponding glass.