Pb1−xSnxF2 layered fluoride super-ionic conductors have become of increased interest for its potential use for all-solid-state secondary fluoride-ion based batteries. By planetary high-energy ball-milling, we have prepared solid-solutions for different stoichiometries: x=0.4–0.6. These materials were investigated by X-ray Diffraction (XRD), Electrochemical Impedance Spectroscopy (EIS), Field Emission Scanning Electron Microscope (FESEM), High-Resolution Transmission Electron Microscope (HRTEM) and Nuclear Magnetic Resonance (NMR) from which a dominant γ-phase (β-PbF2 form) cubic structure with crystal and surface defects have been revealed. Crystallite sizes of around 17nm were achieved. The ionic conductivity of the materials provided a maximum for x=0.45 reaching a value of 2.5·10−3 S·cm−1 at room temperature, with an activation energy of 0.30eV. This solid-state fluorite type electrolyte was applied for testing a solid fluoride ion battery assembly consisting of Bi-cathode and CeF3-anode.