Ceramic powder, such as MgO, is added as a binder to prepare the green compacts of molten salts of an electrolyte for a thermal battery. Despite the addition of a binder, when the thickness of the electrolyte decreases to improve the battery performance, the problem with the unintentional short circuit between the anode and cathode still remains. To improve the current powder molding method, a new type of electrolyte separator with porous MgO preforms is prepared and characteristics of the thermal battery are evaluated. A Spherical PMMA polymer powder is added as a pore-forming agent in the MgO powder, and an organic binder is used to prepare slurry appropriate for tape casting. A porous MgO preform with 300 μm thickness is prepared through a binder burnout and sintering process. The particle size of the starting MgO powder has an effect, not on the porosity of the porous MgO preform, but on the battery characteristics. The porosity of the porous MgO preforms is controlled from 60 to 75% using a pore-forming agent. The batteries prepared using various porosities of preforms show a performance equal to or higher than that of the pellet-shaped battery prepared by the conventional powder molding method.