Cyclophanes bearing bisphenol-A, 3,3′-dinitrobisphenol-A and 4,4′-dihydroxybenzophenone as aromatic units and 1,4-dioxabut-2-yne and 1,6-dioxahexa-2,4-diyne units as bridges have been synthesized. The cyclophane from bisphenol-A bearing 1,4-dioxabut-2-yne bridges has been structurally characterized by single crystal X-ray crystallography and the cavity dimensions were obtained. The cavity dimensions obtained by semiempirical calculations (AM1) indicate that these cyclophanes possess nanometer size cavities.