AbstractThe charge‐transfer (CT) spectra of the π‐complexes formed by several π‐acceptors with some polynuclear[2.2]paracyclophanes have been measured. Comparison of these CT complexes with those of model compounds supports the existence of the transannular electronic interactions in the paracyclophane nucleus. The infrared spectra of a number of CT complexes reveal the increase of the electron density on the π‐acceptor molecule in the CT complexes. Some crystalline CT complexes were prepared an