In this work, Sm and Sc co-doped Bi 1−x Sm x Fe 1−y Sc y O 3 (x = 0.00-0.20; y = 0.03) ceramics are fabricated by a rapid liquid phase sintering method, in order to develop single-phase multiferroics with large magnetization and polarization. X-ray diffraction and Raman spectroscopic studies reveal that the ceramics are single-phase with a structural transition from rhombohedral to orthorhombic structures near x = 0.15. Electric and magnetic measurement results indicate that the transition significantly enhances the multiferroic properties, which stems from the Sm/Sc doping induced collapse of space-modulated spin structure and internal structural distortion. At an optimized composition of Bi 0.85 Sm 0.15 Fe 0.97 Sc 0.03 O 3 (x = 0.15), a remanent polarization of 16.5 μC cm −2 , a magnetization 0.2020 emu g −1 , and a magnetodielectric effect of 0.46% can be obtained. These results clearly demonstrate a potential application for Sm/Sc doped BiFeO 3 ceramics in the field of multiferroic devices.