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CSZM compounds were synthesized by dry chemistry route with 5, 10, and 15% dopant of Mg dopants in the Ce _0.8−2x Sm _0.2 Zr_x Mg_x O_2−d, {x = 0.05, 0.1 & 0.15}. The newly investigated materials were physically, chemically, and electrochemically studied and have shown promising results. The CSZM was crystalized in a fluorite structure with a pure cubic phase in a space group Fm3m and cell parameter a = 5.401742 <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><mo>°</mo><mi>A</mi></mrow></semantics></math></inline-formula> and theoretical density from 7.6 to 8.9 after firing in the air with a final temperature of 1400 °C. Characterization of the structure and indexing of electrolyte materials were made after X-ray diffraction (XRD) testing. A Scanning electron microscope (SEM) morphological analysis was used to examine the microstructure details. Electrochemical impedance spectroscopy (EIS) measurements were performed from 400 °C to 700 °C which show the highest conductivity value of 1.0461 × 10⁺¹ S/cm at 700 °C. In comparison, the minimum value was 2.7329 × 10⁻² S/cm at 400 °C, and the total activation energy (E_a<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><mo>°</mo><mi>A</mi></mrow></semantics></math></inline-formula>) was found to be 0.6865 eV under 5% H₂/Ar.