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 gamma-phase (beta-PbF2 form) cubic structure with crystal and surface defects have been revealed. Crystallite sizes of around 17 nm 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 0.30 eV. This solid-state fluorite type electrolyte was applied for testing a solid fluoride ion battery assembly consisting of Bicathode and CeF3-anode.