[2.2]Paracyclophane is a prevalent π‐stacked, carbocyclic scaffold with a “bent and battered” structure. This results not only in a transannular communication but also in a chiral plane within the molecule if at least one substituent is present. These unique properties make this structure synthetically challenging but also scarcely investigated. A new method for enantio-separation based on kinetic resolution was developed, which allows the access to enantiomerically pure [2.2]paracyclophane-based building blocks. In a liquid crystal templated chemical vapor deposition process, [2.2]paracyclophanyl alcohols containing an additional central chiral element were evaluated for the self-assembly of nanofibers. Furthermore, the cyclopropanation of α-alkyl-α-diazo compounds with a [2.2]paracyclophane-based rhodium tetracarboxylate complex was investigated. Finally, the rigidity, regioselective functionalization, and transannular communication of [2.2]paracyclophane were exploited in the design of heterobimetallic Au(I)/Ru(II) complexes for the study of metal-to-metal interactions.