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At room temperature solid electrolyte Li3−xSc2−xZrx(PO4)3 (x = 0, 0.1) compounds belong to monoclinic symmetry (space group P21/n) and the compound with x = 0.2 belongs to orthorhombic symmetry (Pbcn). At 900 K all the investigated compounds belong to orthorhombic symmetry (space group Pbcn). Anomalies of enthalpy, change of activation energy of ionic conductivity, anomalies of dielectric permittivity in the temperature range 420 K–660 K of investigated compounds with x = 0 and 0.1 were found. The phenomena are related to structure phase transition in the compounds. The relaxation dispersion regions were found in conductivity spectra for the all investigated samples. The frequency dispersion regions are caused by the relaxation processes in grain, grain – boundaries and electrodes. The temperature dependencies of the bulk conductivity and relaxation frequency in the bulk are governed by the same activation energy. It is shown that major role in the temperature dependence of bulk conductivity is played by Li+ ion mobility, which increases as temperature increases. [ABSTRACT FROM PUBLISHER]