The crystal structure and piezoelectric and magnetic properties have been studied in Bi1‒x Sm x FeO3 solid solutions with the compositions near the morphotropic boundary between rhombohedral and orthorhombic (Rh–Orh) phases. The coexistence areas of rhombohedral and antipolar orthorhombic phases, as well as the evolution of structural phases at the interface, have been established. A maximum piezoelectric signal is found for the two-phase composition with the dominating rhombohedral phase, and an increase in the piezoresponse is caused by the decreasing structural stability of the sample. The evolution of magnetic properties in Bi1–x Sm x FeO3 compounds has been elucidated depending on the substitutional ion concentration. The orthorhombic phase composites are the weak ferromagnetics with the residual magnetization of ~0.2 emu/g.