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The electrical properties of 0.65Pb(Mg1/3Nb2/3)O3-0.35(PbTiO3) ceramics over a wide range of frequencies (102–106 Hz) and temperatures (30–225∘C) were studied using impedance spectroscopy technique. The impedance and electric permittivity were strongly temperature and frequency dependent. The activation energy, calculated from the temperature dependence of AC conductivity of the ceramics was found to be ∼0.5 eV. The relaxation process in the ceramics was found to be of non-Debye type. The nature of Cole-Cole diagram reveals the contribution of grain (bulk) and grain boundary permittivity in the ceramics.