The diffusion couples of lanthanum based strontium borosilicate glass with two different (high and low temperature) electrolytes have been heat-treated at 850 and 800 °C, respectively, for 5, 100, and 750 h to understand the mechanism of interface formation and growth. These prepared diffusion couples have been characterized using various techniques like X-ray diffraction (XRD), scanning electron microscope (SEM), X-ray dot mapping, and electron probe microanalysis (EPMA). XRD revealed no detrimental phase formation. Other thermodynamic parameters like frequency factor, crystallization constants, free volume, and bulk thermal expansion coefficients have been calculated to understand the behavior of glass under the influence of temperature. These theoretical parameters will enable to understand the interfacial growth observed in heat-treated couple for its end application in SOFC. The observed results indicate that lanthanum containing glass exhibit stable and smooth interface with yttria-stabilized zirconia (high-temperature electrolyte) as compared to doped bismuth vanadate (low temperature electrolyte).