BiFeO3-based composite materials are important due to their versatile multiferroic properties which can be further tuned upon doping. 0.5BiNdxFe1-xO3-0.5PbZrO3 (x = 0.05, 0.1, and 0.2) polycrystalline ceramic samples were prepared by solid-state reaction technique at high temperature. X-ray diffraction (XRD) and Rietveld refinement process confirm the presence of mainly rhombohedral (R3c) phase. Dielectric studies reveal the presence of Maxwell-Wagner type polarization. Electric impedance and modulus values of the samples were studied over a wide range of temperature and frequency. Complex impedance and modulus studies shows the presence of non-Debye type of relaxation in the materials. ac conductivity results can be fitted with Jonscher’s power law and indicates the dominance of correlated barrier hopping mechanism in charge transport. Furthermore, density of states calculated from ac conductivity shows variation as a function of dopant content which is further corroborated from density functional theory-based results.