This study examines the impact of doping Tb3⁺ ions into Ca12Al14O33 to analyze its structural and luminescent properties for potential use in plasma display panels (PDPs). Phosphors were synthesized via the sol–gel method and characterized using XRD, FT-IR, SEM, and PL techniques. Morphological observations via SEM revealed micron-sized, irregularly shaped particles, outlining the distinct morphology of the material. Luminescence investigations revealed an improved energy transfer process apparent in the emission and excitation spectra. Under ultraviolet (UV) and vacuum ultraviolet (VUV) excitation, the predominant green emission at 543 nm, attributed to the 5D4 → 7F5 transition of Tb3+ ions, exhibited optimal luminescent properties up to a Tb3+ concentration of 0.07 mol. However, the subsequent decrease in emission intensity beyond this threshold occurred due to a concentration-quenching effect. Further analyses demonstrated vacuum photoluminescence at 147 nm and 172 nm, exhibiting robust green emissions at 543 nm associated with the 5D3, 5D4 → 7FJ transitions inherent to Tb3+ ions. Moreover, all samples exhibited color purity ranging from 85 to 95%. The exceptional luminescence attributes of Ca12Al14O33:Tb3+ signify its potential in diverse applications. Notably, its promising applicability in PDP stems is due to its specific emission peaks and luminescent behavior. This study presents avenues for future research, emphasizing potential optimization strategies for PDP applications and exploring the properties of phosphors across various technological domains.