The structural and vibrational properties of 5% Sm-substituted BiFeO3 under pressure are investigated using synchrotron X-ray diffraction and Raman scattering measurements. The results yield the pressure-induced structural phase transitions from the polar R3c phase to the orthorhombic Pnma phase commencing at 3.9 and being complete at 7.6GPa, where there is a region of the coexistence of the R3c and Pnma phases. This structural transition is companied by the ferroelectric-paraelectric transition for the Sm-substituted BiFeO3. We find that the Sm substitution leads to lower transition pressure compared to that of the pure BiFeO3 system due to the substitution-induced chemical pressure. Our results do not suggest the pressure-induced reentrance of ferroelectricity in the model multiferroic BiFeO3 in the pressure range studied. (C) 2013 AIP Publishing LLC.