Up to now, the thermal expansion behavior of multiphase glass-ceramics cannot be predicted reliably because of the nescience about the formation of the type and concentration of crystalline phases. In the system BaO-SrO-ZnO-SiO2, recently a new phase based on Ba1-xSrxZn2Si2O7 solid solutions was found, which exhibits unexpected low and highly anisotropic thermal expansion, which can be used for an adjustment of the thermal expansion properties. In the case of sealing materials for high-temperature reactors, the formation of this phase should be avoided. Hence, in this manuscript the concentration thresholds in which these solid solutions precipitate from glasses were determined. The phase analysis was correlated with the thermal expansion behavior of the glass-ceramics. Depending on the Ba/Sr-ratio of the glasses and the considered temperature range, the coefficients of thermal expansion of the glass-ceramics vary between 19.4·10-6 K-1 and 4.8·10-6 K-1. The concentration thresholds in which the as mentioned phases form via crystallization of glasses differ strongly from the literature values obtained via conventional ceramic mixed oxide route.