Solid-state electrolytes Na2MTeO6 (M = MgNi and MgZn) were prepared via a conventional solid-state reaction method. Structural properties of the samples were investigated by using powder X-ray diffraction (XRD), Raman, Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy, and X-ray photoelectron spectroscopy (XPS) techniques. XPS and XRD studies indicate the phase pure hexagonal layered P2-type structure of samples. Raman and FTIR spectroscopy reveal the possible bending and stretching vibration modes for Te–O and other metal oxides. The ion transport properties of the solid electrolytes were investigated by using AC impedance spectroscopy. The electrical properties were examined by means of classical brick layer model. The specific grain conductivity (σg) is found to be 2.13 × 10−5 S cm−1 and 0.90 × 10−5 S cm−1 at 20 °C for Na2MgNiTeO6 and Na2MgZnTeO6 electrolytes, respectively. The activation energy of σg for Na2MgNiTeO6 and Na2MgZnTeO6 is found to be 0.59 eV and 0.36 eV respectively for the temperature below 30 °C. Summerfield AC conductivity scaling analysis of samples is performed. These electrolytes could be potential candidates in solid-state Na+ battery applications.