Core-shell-based nanomaterials have garnered considerable attention in the recent past not only in catalytic applications but also in their potentiality in selective and efficient sensing. Present research reports the first and successful biosynthesis of the core (c-Al2O3)-shell nanoparticles (NPs) using Bauhinia variegate blossom extract as reducing and capping agents. The synthesized c-Al2O3 NPs were characterized and utilized to fabricate nanobioengineered electrodes on indium tin oxide (ITO) substrates via electrophoretic deposition. Electrochemical analysis, including cyclic voltammetry and differential pulse voltammetry, revealed quasi-reversible processes with high electron-transfer rates (Ks = 0.66 s-1) and a diffusion coefficient (D = 5.84 × 10-2 cm2 s-1). The electrode exhibited a very high sensitivity (23.44 μA μM-1 cm-2) and a low detection limit (0.463 μM) for sodium azide (NaN3) over two linear ranges of 1-6 and 8-20 μM. Additionally, c-Al2O3 NPs demonstrated the effective photocatalytic degradation of crystal violet dye under visible light, following pseudo-first-order kinetics. The fabricated electrode showed excellent selectivity, stability, and reproducibility, highlighting its potential for environmental monitoring and clinical diagnostics.