The nanoscale samples of Pb0.90La0.10(Ti1-x Mn (x) )(0.975)O-3 (x = 0.0, 0.04, 0.07, and 0.10) compounds were prepared using high-energy ball-milling method. Thermo-gravimetric analysis and high-resolution X-ray diffraction studies were carried out to verify the phase formation. Single-phase compounds were formed exhibiting tetragonal system. The presence of impedance and modulus spectroscopic data was used to gain an insight into the electrical properties of the samples and with a view to observing the relaxations in them. Impedance studies show non-freq-type behavior and the relaxation frequency shift toward higher frequency side with increase in temperature. An equivalent circuit has been used to provide a complete picture of the material. The difference between localized (i.e., dielectric relaxation) and non-localized conduction (i.e., long-range conductivity) processes within the bulk of the material may be discerned by the presence or the absence of a peak in the imaginary impedance and modulus versus frequency plot.