New crownophanes containing 2,7-dioxy-fluorenone and 4,4′-azobiphenoxy moieties linked by di-, tri-, tetra-, and pentaethylene glycol residues were synthesized. Just in case of obtaining largest crownophane with pentaethyleneglycol linkers, the dimeric cyclization product was also isolated in low yield. Obtained crowno-phanes, according to ¹H NMR spectral data exist in conformations with closed intramolecular cavity in solution. Photoinduced E-Z isomerization of crownophane containing triethylene glycol linkers were investigated. The azobenzene fragment inclusion into crownophane reduces the photoisomerization rate compared to model 4,4′-dimethoxyazobenzene. In all the obtained crowno-phanes according to NMR, UV-Vis and X-ray data 4,4′-azobiphenoxy fragment is in E-configuration in solution as well as in the solid state. Crystal packing of all crownophanes has distinct feature-stacking arrangement of fluorenone moieties probably due to electrostatic dipole-dipole interactions. The formation of pseudorotaxane-type host-guest complexes of these crownophanes with paraquat dication was detected by FABMS and ¹H NMR spectroscopy. UV-Vis spectra show no significant changes upon complex formation.