Abstract. Ba2ScSbO6 (BSS) has been synthesized in polycrystalline form by solid state reaction at 1400 ˚C for 72 Hrs. Structural characterization of the compound was done through X-ray diffraction (XRD) followed by Riedvelt analysis of the XRD pattern. The crystal structure is cubic, space group Fm-3m (No. 225) with the lattice parameter, a = 8.230 Ǻ. Optical bandgap of the present system has been calculated using the UV-Vis Spectroscopy and Kubelka-Munk (KM) function, it's value being 4.2eV. A detailed study of the electronic properties has also been carried out using the Full-Potential Linear Augmented Plane Wave (FPLAPW) as implemented in WIEN2k. BSS is found to be a large band-gap insulator with potential technological applications, such as dielectric resonators and filers in microwave applications.