Lithium triborate LiB₃O5:Eu has been prepared by precipitation assisted high-temperature solid state (PAS) reaction method using lithium hydroxide (LiOH), boric acid (H₃BO₃) and europium chloride (EuCl₃). The as prepared powders were calcined at various temperatures. As prepared and calcined powders were characterized by X-ray diffraction (XRD), Scanning Electron Microscopy (SEM), Energy Dispersive X-ray Spectrometry (EDS), UV-Vis spectrometry and Photoluminescence (PL). The XRD profiles of the powder products revealed the presence of crystalline phase at 650 °C. Increasing bandgap with increasing dopant concentration was studied by UV-Vis spectra. The effect of dopant concentration on photoluminescence properties of LiB₃O5 was also studied. The optimized Eu3+ dopant concentration for potential luminescent LiB₃O5 phosphor was 0.25 mol%.