Tin‐based halide perovskite solar cells can be efficient and environmentally friendly substitutions to lead‐based halide perovskite solar cells, but they have a drawback due to oxidation from Sn 2+ to Sn 4+ . Using vacuum deposition, epitaxially aligned CsSnBr 3 ultrathin films are prepared on Au(111) and Au(100) and characterized with scanning tunneling microscopy (STM), low‐energy electron diffraction (LEED), and X‐ray photoelectron spectroscopy (XPS). By co‐evaporation of the precursor molecules CsBr and SnBr 2 , few monolayers of perovskite are obtained. On Au(111), CsSnBr 3 grows in three differently oriented domains due to the hexagonal symmetry of the substrate. On Au(100), which has square symmetry, identical to CsSnBr 3 , but with about half the lattice constant of the perovskite, a (2×2) superstructure is observed. The perovskite is terminated with the (001) facet showing a square surface structure in agreement with density functional theory (DFT) calculations. Chemical analysis is performed in ultra‐high vacuum (UHV) conditions and no indication of a tin oxidation state higher than Sn 2+ is found in the films. However, after exposure to air, rapid and severe changes in the films are observed, highlighting the importance of preparing tin perovskites in a controlled environment to maintain their stability and avoid oxidation‐related issues.
