In this study, we introduce a Na β″-alumina composite thick film as a solid electrolyte, to reduce the resistance of electrolyte for a Na/S battery. An alumina/zirconia composite material was used to enhance the mechanical properties of the electrolyte. A solid electrolyte of about 40 μm thick was successfully fabricated through the conversion and tape-casting methods. In order to investigate the effect of the surface treatment process of the solid electrolyte on the battery performance, the electrolyte was polished by dry and wet processes, respectively, and then the Na/S batteries were prepared for analyzing the battery characteristics. The battery with the dry process performed much better than the battery made with the wet process. As a result, the battery manufactured by the dry process showed excellent performance. Therefore, it is confirmed that the surface treatment process of the solid electrolyte has an important effect on the battery capacity and coulombic efficiency, as well as the interface reaction.