Reactions of 4‐ethenyl[2.2]paracyclophane (3) and its derivatives or of 4‐ethynyl[2.2]paracyclophane (27) with benzyne (4) afforded [2.2](1,4)phenanthrenoparacyclophanes 2, 7, and 9. The diethenyl[2.2]paracyclophanes 16, 19 and 22 reacted with 4 to give the stereoisomeric phenanthrenophanes 18, 21 and 23, respectively. The NMR spectra, in particular the 1H chemical shifts, of the diethenylparacyclophanes, the [2.2]phenanthrenoparacyclophanes and the [2.2]phenanthrenophanes are discussed.