Un-doped and ZnAlxO(1.5x + 1):0.1% Tb3+ (ZAOT) nano-powders were synthesized via citrate sol-gel method. The Alx moles were varied in the range of 0.25 ≤ x ≤ 5.0. The X-ray powder diffraction (XRD) data revealed that for the x < 1.5, the prepared samples crystal structure consists of mixed phases of the cubic ZnAl2O4 and hexagonal ZnO phases, while for the x ≥ 1.5 the structure consists of single phase of cubic ZnAl2O4. This was confirmed by the Raman and Fourier-Transform Infrared (FTIR) vibrational spectroscopy. Scanning electron microscopy (SEM) showed that varying Alx moles influences the morphology while Transmission electron microscopy (TEM) shows the dual morphology at x < 1.5. The photoluminescence (PL) revealed intense and distinct emissions attributed to both the host and Tb3+ transitions. The emission intensity highly depends on the Alx moles. The International Commission on Illumination (CIE) colour chromaticity showed that the emission colour could be tuned by varying the Alx moles.