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Air‐stable p‐type SnF₂:Cs₂SnI₆with a bandgap of 1.6 eV has been demonstrated as a promising material for Pb‐free halide perovskite solar cells. Crystalline Cs₂SnI₆phase is obtained with CsI, SnI₂, and SnF₂salts in gamma‐butyrolactone solvent, but not with dimethyl sulfoxide andN,N‐dimethylformamide solvents. Cs₂SnI₆is found to be stable for at least 1000 h at 100 °C when dark annealed in nitrogen atmosphere. In this study, Cs₂SnI₆has been used in a superstrate n–i–p planar device structure enabled by a spin‐coated absorber thickness of ≈2 μm on a chemical bath deposited Zn(O,S) electron transport layer. The best device power conversion efficiency reported here is 5.18% withV_OCof 0.81 V, 9.28 mA cm⁻²J_SC, and 68% fill factor. The dark saturation current and diode ideality factor are estimated as 1.5 × 10⁻³ mA cm⁻²and 2.18, respectively. The devices exhibit a highV_OCdeficit and low short‐circuit current density due to high bulk and interface recombination. Device efficiency can be expected to increase with improvement in material and interface quality, charge transport, and device engineering.