The present work reports the analysis of temperature‐dependent electrical and conductivity studies on Ca2+ doped BiFeO3 multiferroic ceramics in the temperature range of 300–600 K. The effect of Ca2+ doping on the impedance and modulus behavior of BiFeO3 lattice is discussed. The observed changes as a function of increasing Ca2+ concentration have been explained using the change in crystal unit cell. It is also shown that the microstructure changes significantly as a function of Ca2+ concentration. The grain and grain boundary effects in determining the impedance behavior is also reported in the paper.