The porphyrin‐bridged cyclophane 1 was prepared in order to mimic monooxygenase activity and serve as a supramolecular catalyst for the hydroxylation of polycyclic arenes. In methanol, arenes such as anthracene, ace‐naphthylene, and phenanthrene are firmiy complexed in the nonpolar interior of 1. In 2,2,2‐trifluoroethanol in the presence of iodobenzene, the iron(III) derivative 2 catalyzes the oxidation of acenaphthylene to ace‐naphthen‐1‐one (65% yield). (Figure Presented.) Copyright © 1990 by VCH Verlagsgesellschaft mbH, Germany