Misfit strain, polarization, permittivity, and tunability of Ba
x
Sr1−x
TiO3 (BST) thin films on various substrates with varied buffer layers are calculated by a modified thermodynamic model. The lattice parameters of the LaAlO3 (LAO), CaTiO3 (CT), BaZr0.25Ti0.75O3 (BZT), and MgO buffer layers grow consecutively as does the thermal expansion coefficient (TEC) of the Si, Ti, Ni, and stainless steel (SS) substrates. When the TEC of substrates is bigger (such as Ni, SS) than that of the films, introducing buffer layers with larger lattice parameters (such as BZT, MgO) can improve the permittivity and tunability. Conversely, inserting buffer layers with smaller lattice parameters (such as LAO, CT) can enhance the dielectric response when the TEC of substrates is smaller (such as Si, Ti) than that of the films. The relationship between the TEC of substrate and the lattice parameter of buffer layer is primarily linear for achieving high tunability. According to several references, introducing LaNiO3 buffer layers can significantly increase the tunability of BST solid solutions prepared on Si‐based substrates, which is in line with the estimated rule. This law offers a guide for choosing the best substrate and buffer layer when producing BST films with strong dielectric response.