The Na2Zn0.5Mn0.5P2O7 powder was prepared by the solid state reaction method. The powder structure was studied by X-ray diffraction (XRD) in the temperature range from room temperature (RT) to 520 K. The results of XRD measurements show that the obtained Na2Zn0.5Mn0.5P2O7 is a mixture of two phases: Na2MnP2O7, which crystallizes in the triclinic space group P–1, and Na2ZnP2O7, which crystallizes in the tetragonal space group P42/mmm. The chemical compositions of the powder and ceramic samples were investigated by an energy dispersive X-ray spectrometer (EDX) and X-ray fluorescence spectroscopy (XFS). The surface of ceramics was examined by X-ray photoelectron spectroscopy (XPS). The electrical conductivity and dielectric permittivity of the ceramics were investigated from RT to 700 K in the frequency range 10–109 Hz. The relaxational dispersion of electrical conductivity in the investigated frequency and temperature range was found.