Abstract <p>Multiferroic (1 – <i>x</i>)BiFeO₃–<i>x</i>PbTiO₃ binary ceramics series exhibit interesting features such as tetragonality <i>c</i>/<i>a</i>, polarization, and high Curie temperature. The composition with <i>x</i> = 0.3 possesses a morphotropic phase boundary (a boundary separating rhombohedral and tetragonal phases). This is a very fascinating character of this composition as it exhibits two ferroic orderings which result in the enhancement of the ferroelectric properties of the system. The structural information related to this system is very crucial to predict the ferroelectricity in this compositional series. Goldschmidt’s tolerance factor is one of the important aspects to determine the stability of the perovskite (ABO₃ type crystal) structure. In the present case, polycrystalline 0.7BiFeO₃–0.3Pb_1–<i>x</i>Sr_<i>x</i>TiO₃ compositions with <i>x</i> = 0, 0.2, 0.4, 0.6, 0.8, and 1.0, were selected to determine the effect of Sr²⁺ substitution at the Pb-site in the composition, and the comparative correlation studies were conducted for ferroelectric ordering in the system.</p>