In this review, the state of the art in understanding the structural phase relations in perovskite-structured BiFeO3-based polycrystalline solid solutions is presented and discussed. Issues about the close relation between the structural phase and overall physical properties of the reviewed systems are pointed out and discussed. It is shown that, by adjusting the structural symmetric arrangement, the ferroelectric and magnetic properties of BiFeO3-based polycrystalline solid solutions can be tuned to find specific multifunctional applications. However, an intrinsic mechanism linking structural arrangement and physical properties cannot be identified, revealing that this subject still deserves further discussion and investigation.