The lower rim functionalized hexahomotrioxacalixarene derivatives cone-3 and cone-5 bearing three benzyl and three N,N-diethyl-2-aminoethoxy groups, respectively, were synthesized from triol 1. Their complexation with 2-(3,4-dihydroxyphenyl)ethylamine (dopamine), 5-hydroxytryptamine (serotonin), and 2-phenylethylamine (phenethylamine), which have biologically important activities, has been studied by 1H-NMR spectroscopy. The chemical shifts of the aromatic protons of the host and guest molecules and the up-field shifts of the ethyl protons of the guest molecules strongly suggest the formation of inclusion complexes in solution. The formation of the host–guest complexes is assisted by a hydrogen bond and/or an electrostatic interaction between the host and ammonium ion (RNH3+) of the guest. The structures of receptors cone-3 and cone-5 have been determined by X-ray crystallography.