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A novel two-phase mixed oxide-ion and carbonate-ion conductor (MOCC) has been recently developed for intermediate temperature solid-oxide fuel cells and CO₂ separation membranes. With conventional mixing–pressing ceramic fabrication technique it is difficult to obtain a MOCC with high mechanical strength and high oxide-ion conductivity due to the low sintering temperature. In this study, a samarium doped ceria (SDC, Ce_0.8Sm_0.2O_1.9) is selected to demonstrate the prefabrication of porous matrix by the “sacrificial template” methodology with Ni as the template material. The microstructure of the SDC matrix characterized with a 3D X-ray computed tomography and a SEM imaging reveals a uniform distribution of homogeneous micro-pores across the solid-oxide matrix. A Li–Na-carbonate-impregnated MOCC supported by a 40% porous SDC matrix shows an effective ionic conductivity of 0.55 and 0.46S/cm …