The dielectric behavior and structure of the Sr(Zn1/3Nb2/3)O3-Ba(Zn1/3Nb2/3)O3 solid solution have been investigated with the intention of understanding the relationship between the structural changes and the temperature coefficient of the relative permittivity τε. A correlation between the value of τε and the occurrence of O-octahedra tilts has been established. The occurrence of ferroelastic domains and their influence on τε has also been investigated. It is proposed that the results obtained can be used to generalize about the structure-property relationships in compounds of the same class.