The protonated forms of the chiral molecules (S)- and (R)-N-benzyl-1-(1-naphthyl)ethylamine (BNEAH+) form very stable 1:1 guest–host complexes with cucurbit[7]uril in aqueous solution. The stoichiometry and stability constants for the guest–host complexes were determined by 1H NMR, UV–visible and circular dichroism spectroscopy and electrospray mass spectrometry. The molecular optical rotations of the guests increase in magnitude by about 5-fold upon formation of the {BNEAH·CB[7]}+ species. Energy minimized structures of the guests and guest–host complexes indicate changes in the dihedral angles about the stereogenic centre upon ion-dipole and H-bonding interactions between the ammonium hydrogens of the guest and the carbonyl groups of the cucurbituril portals. The increases in the optical rotations are discussed in terms of restricted rotations of the naphthyl groups and in preferential solvation of benzylamine in the cucurbit[7]uril cavity.