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A Ba-based glass-ceramic sealant is designed and tested for solid oxide electrolysis cell (SOEC) applications. A suitable SiO2/BaO ratio is chosen in order to obtain BaSi2O5 crystalline phase and subsequently favorable thermo-mechanical properties of the glass-ceramic sealant. The glass is analyzed in terms of thermal, thermo-mechanical, chemical, and electrical behavior. Crofer22APU-sealant-Crofer22APU joined samples are tested for 2000 h at 850 °C in a dual atmosphere test rig having reducing atmosphere of H2:H2O 50/50 (mol%) and under the applied voltage of 1.6 V. In order to simulate the SOEC dynamic working conditions, thermal cycles are performed during the long-term electrical resistivity test. The glass-ceramic shows promising behavior in terms of high density, suitable CTE, and stable electrical resistivity (106–107 Ω cm) under SOEC conditions. The SEM-EDS post mortem analysis confirms excellent chemical and thermo-mechanical compatibility of the glass-ceramic with Crofer22APU.