The structural and spectroscopic properties of Barium tetraborate crystals activated with Eu3+ ion have been studied. Differential thermal analysis, X-ray diffraction (XRD), and SEM techniques have been used for structural characterization. The XRD pattern revealed the formation of alpha-BaB4O7 crystals. It was observed that under the proposed charge compensation model, the structural properties of the alpha-BaB4O7 crystal significantly alter the luminescence characteristics of Eu3+ and Eu2+ ions. The enhancement of the emission explained and the photo-physics involved is correlated with the unique structural properties of the crystallites formed.