Abstract Polycrystalline BiFe1-xScxO3 (x = 0, 0.05, 0.10 and 0.15) compounds were prepared using solid state reaction route. The X-ray diffraction patterns showed that Sc substitution stabilized the crystal structure in rhombohedral structure with R3c space group along with nominal percentage of monoclinic structure with Cm space group. Raman and FTIR measurements revealed that the substituent replaced Fe-ions and caused structural distortions. Co-existence of ferroelectric and antiferroelectric phases were observed in Sc substituted BiFeO3 and antiferroelectric phase is found to be evolved at the expense of ferroelectric phase with the Sc content. The electric field driven effects indicated that antiferroelectric phase was suppressed and ferroelectric phase was enriched. Frequency dependence of dielectric constant (εr) and dielectric loss tangent (tan δ) at different temperatures were investigated. Further, grain resistances and grain boundary resistances were increased with the Sc content. Activation energies estimated from dielectric, impedance and modulus data indicated that these relaxations originated presumably due to the oxygen vacancy movements. © 2015 Elsevier B.V. All rights reserved.