<p>Zirconia-based materials find widespread use in a range of technological applications, including oxygen sensors, solid-oxide fuel cell (SOFC) electrolytes, resistive heating elements, balls/jars, dental applications, turbine engine, thermal barrier coatings, and refractory linings for high-temperature furnaces. There are three distinct allotropic phases of zirconia—monoclinic, tetragonal, and cubic—which are stable below approximately 1170°C, 2370°C, and the melting point (2715°C), respectively. The cubic form can also stabilize at room temperature via a suitable dopant. Yttria-stabilized zirconia, a ZrO₂-Y₂O₃ solid solution that contains a large numbers of oxygen vacancies at higher temperature, is extensively used in energy and industrial applications. The fast diffusion of oxygen ions is widely recognized in yttria-stabilized zirconia (cubic fluorite structure), which makes it material of interest for use in electrochemical applications. The structure–property relationship and electronic structure calculation of cubic yttria-stabilized zirconia (YSZ) solid electrolyte are crucial for understanding its performance in various applications, particularly in SOFCs and other electrochemical devices. Therefore, in this paper, we investigate the crystal structure using X-ray diffraction (XRD), the microstructure using scanning electron microscopy (SEM), and the electronic structure via computational analysis of cubic zirconia (YSZ), in order to establish a correlation with the dielectric and electrical properties at elevated temperatures, along with ion-conducting channel study via electron density maps using GFourier analysis.</p>