In this paper, detailed studies of effect of small amount of manganese substitution (at the zirconium site) on the structural, micro-structural, and electrical characteristics of lead zirconate titanate of Pb(Zr0 .35–x Mn x Ti0 . 65)O3; x = 0, 0.02, 0.06, 0.10 (PZMT)) have been reported. The materials were prepared by using standard ceramic technology. The formation of the compounds and their basic crystal data have been studied through X-ray diffraction (XRD) method. The crystallite size and lattice strain of the compounds, evaluated from Scherrer’s and Hall Williamson (H-W) equations, is found to be in the range of 40–50 nm and 11 × 10−4 to 50 × 10−4, respectively. Microstructures of different magnifications, revealing the surface nature of the compounds, have been recorded by field emission scanning electron microscope (FESEM). Effect of Mn+4 ions on electrical behavior (electrical impedance (Z*), electrical modulus (M*), conduction and relaxation phenomenon) of PZMT systems, over wide range of temperature and frequency, has been studied.