<p>All-solid-state Fluoride-ion batteries (ASSFIBs) are recognized as an alternative of “post lithium-ion” battery systems due to the advantages of abundant fluorine resources, high theoretical volumetric energy density, and intrinsic safety. However, the development of ASSFIBs is still blocked by several obstacles, such as low ion conductivity of solid-state electrolyte at room temperature, harsh charge transfer between interfaces of electrodes and electrolyte, and etc. This research utilizes NH₄Sn_1.96Zr_0.04F_5.08 as the solid-state electrolyte for the advantages of high room-temperature ionic conductivity, low cost, and easy synthesis processes. The NH₄Sn_1.96Zr_0.04F_5.08 fabricated by simple mechanochemical method provides two-dimensional diffusion channels for F⁻ ions between Sn-F layers and NH₄⁺ layers. Besides, the doping Zr⁴⁺ further regulates F⁻ concentration/vacancies in NH₄Sn_1.96Zr_0.04F_5.08 for ion transfer and cycling stability. The as-assembled NH₄Sn_1.96Zr_0.04F_5.08 worked with Ag and PbF₂-Pb electrodes achieves an ionic conductivity of 5.12 × 10^− 4 S cm^− 1 and an initial discharge capacity of 284.4 mAh g^− 1 at 6 mA g^− 1 and 162.1 mAh g^− 1 at 100 mA g^− 1, and remains 88.4 mAh g^− 1 at 20 mA g^− 1 after 80 cycles at room temperature.</p>