The aim of the present work is to investigate the effect of BaO on the thermal behavior, crystallization and properties of magnesium alumino borosilicate-based glasses and glass-ceramics. La2O3 has initially been added to the glass systems as it is known to control the viscosity, crystallization of the borosilicate glasses with a simultaneous improvement of mechanical property of the bulk glass. The glass forming zone have been identified with least possible amount of BaO to accomplish the target of CTE matching with YSZ and Crofer22APU, using only B2O3 as the glass former. After optimization of BaO content in the glass, SiO2 has been gradually added to the glass in form of different SiO2:B2O3 ratios as B2O3 is known to be highly volatile at the SOFC environment [37]. Finally, within the composition ranges, an optimum composition has been identified based on its thermal behavior, change of CTE as a function of time upon heat-treatment at the operating temperature (800 °C), mechanical properties, leak-rate, bonding characteristics in sandwiched condition and minimum chemical interaction with the metallic interconnect.