The first three representatives of the new family of oxacyclophanes incorporating two 2,7-dioxyfluorenone fragments, connected by [-CH ₂CH₂O-]_m spacers (m=2-4), have been synthesized. The yield of the smallest oxacyclophane (m = 2) is considerably higher with respect to the larger ones (m = 3 and m = 4), which are formed in comparable yields. Molecular modeling and NMR spectra analysis of the model compounds suggest that an essential difference in oxacyclophanes yields is caused by formation of quasi-cyclic intermediates, which are preorganized for macrocyclization owing to intramolecular π-π stacking interactions between the fluorenone units. The solid-state structures of these oxacyclophanes exhibit intra- and intermolecular π-π stacking interactions that dictate their rectangular shape in the fluorenone backbone and crystal packing of the molecules with the parallel or T-shape arrangement. The crystal packing in all cases is also sustained by weak C-H⋯O hydrogen bonds. FAB mass spectral analysis of mixtures of the larger oxacyclophanes (m = 3 and m = 4) and a paraquat moiety revealed peaks corresponding to the loss of one and two PF ₆^- counterions from the 1:1 complexes formed. However, no signals were observed for complexes of the paraquat moiety with the smaller oxacyclophane (m=2). Computer molecular modeling of complexes revealed a pseudorotaxane-like incorporation of the paraquat unit, sandwiched within a macrocyclic cavity between the almost parallel-aligned fluorenone rings of the larger oxacyclophanes (m = 3 and m = 4). In contrast to this, only external complexes of the smallest oxacyclophane (m = 2) with a paraquat unit have been found in the energy window of 10 kcal mol^-1.