Polycrystalline BiFeO3and 0.90BiFeO3-0.10Bi0.5Na0.5TiO3compounds were synthesized by conventional solid state route. The compounds were crystallized in rhombohedral structure with R3c space group. Complex impedance studies revealed that insulating character of both grain and grain boundaries were improved in 0.90BiFeO3-0.10Bi0.5Na0.5TiO3compound. Both complex and modulus plots confirmed the presence of non-Debye type relaxations in these compounds. Frequency dependence of AC conductivity at different temperatures suggests that charge carriers follow correlated barrier hopping (CBH) model. Estimated activation energies indicated that oxygen vacancies movements are the prime contributors to the conduction in the measured temperature range. © 2015 AIP Publishing LLC.