ABSTRACT The functional properties of metal‐organic framework (MOF) thin films crucially depend on their structure, which is often difficult to determine. A widely investigated material is Cu(bdc) (bdc = benzene‐1,4‐dicarboxylic acid) grown from solution, for which various thin‐film structures have been suggested. Unfortunately, none of them represents a (meta)stable polymorph and is simultaneously consistent with the material's ferromagnetic nature, the difficulty of loading guest molecules, an