Pb1-xSmx(Zr0.45Ti0.55)1-x/4O3 (PSZT; x = 0.00, 0.03 and 0.06) ceramic samples were prepared by high temperature mixed oxide method. Using complex impedance spectroscopy (CIS) technique, the complex impedance (Z*) and modulus (M*) properties of the materials were analyzed within a wide range of temperature and frequency. Impedance analysis indicates the presence of mostly bulk resistive (grain) contributions which is found to decrease with the increase in temperature. It suggests about the negative temperature coefficient of resistance (NTCR) type behaviour of the materials. Complex modulus plots exhibit the presence of grain (bulk) as well as grain boundary contributions in the materials and also support their NTCR type behaviour. Both the complex impedance and complex modulus plots confirm the presence of non-Debye type of relaxation in the materials. At higher temperatures, bulk resistance is found to increase with the increase in Sm 3+ concentration in PSZT along with the increase in relaxation phenomenon.