The solid electrolyte Li1+xScxZr2−x(PO4)3 (where x = 0.1, 0.2, 0.3) compounds were synthesized by a solid state reaction and studied by X-ray diffraction at room temperature. At room temperature the investigated compounds belong to rhombohedral symmetry (space group R3c) with six formula units in the lattice. The ceramic samples were investigated by complex impedance spectroscopy in the frequency range from 10 6 to 1.2·10 9 Hz at temperatures ranging from 300 to 600 K. Two regions of relaxation dispersion were found. The dispersions are related to the fast Li + ion transport in the grains and grain boundaries of ceramics. Variation of the stoichiometric parameter affects the density of the ceramics, the values of total and grain conductivity, their activation energies, and frequency of the relaxation processes in the materials. The increase of parameter x leads to the increase of values of total and grain conductivities, dielectric permittivity, and dielectric losses of the ceramics.