We report high structural order in thin films of the organic semiconductor perfluoro‐pentacene (PFP), which is a candidate material for n‐type applications, deposited by vacuum sublimation on oxidized silicon wafers. Bragg reflections up to high order in both specular and grazing incidence geometries and a mosaicity of less than 0.01° demonstrate the well defined structure. The thin film entirely consists of crystallites with a structure close to the bulk phase without any contamination with a second phase. Real‐time X‐ray measurements show that PFP grows in a Stranski–Krastanov growth mode with the first monolayer wetting the substrate before 3d‐growth sets in during growth of the second monolayer. Implications for its use are discussed. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)