Abstract: The ¹³C-NMR and ¹H-NMR spectra of nine benzo-15-crown-5 are recorded. Comibned with microanalyses, infrared, ultraviolet and mass spectroscopy data, the molecular structures of the crowns are determined. All the ¹³C-NMR spectral lines are assigned based on the line positions and splittings as well as substituent inductive effects. The influences of benzine ring's different sub-stituets on the chemical shifts of crown's carbons are also discussed.