The compounds of Pb(Zr0.35-xYxTi0.65)O3 (x = 0.00, 0.10 and Y = Mn/Ce) stoichiometry were prepared by a standard solid state route of mixing. The lead zirconatetitanate (PZT) has been modified by substituting 10% of manganese (Mn+4), and cerium (Ce+4) ions, by replacing zirconium (Zr+4). The effect of substitution of Mn+4 and Ce+4 ions, on the electrical properties of PZT based ceramics, has been investigated systematically in this work. To study the impedance and modulus characteristics, adopted are the complex impedance and complex modulus spectroscopic methods respectively. Results indicated that the compounds exhibit negative coefficient of resistance behavior (as evident from impedance spectra), and real ionic conductor nature (as evident from modulus spectra). The electrical properties of the compounds are primarily dominated by the grains rather than grain boundaries and electrode-material interface polarization.