AbstractDerivatives of 2,2′,7,7′‐tetrahydroxy‐1,1′‐binaphthyl (5) are synthetically readily available chiral shapes with a major and a minor groove. Previous work by Cram et al. has shown that efficient chiral crown ether binding sites can be constructed at the binaphthyl minor groove. The major groove is almost twice as wide and possesses suitable dimensions to shape flat apolar binding sites in chiral cyclophane hosts. The eight‐step syntheses of the two novel cyclophanes 6 and 7 are described. The apolar cavities of these hosts are formed by bridging with two linear four‐carbon chains the 7,7′‐oxygens at the major groove of 5 to the two phenolic oxygens of a 4,4‐bis(4‐hydroxy‐3,5‐dimethylphenyl)piperidine unit. 1H NMR complexation studies show that 1:1 complexes of 6 and 7 with 6‐methoxy‐2‐naphthonitrile and other naphthalene derivatives in aqueous methanol are as stable as the previously reported complexes of bis(diphenylmethane)‐hosts. The different solvation characteristics of cation and apolar binding are demonstrated with the ditopic host 7. In addition to the apolar binding site at the major groove, 7 also possesses a crown ether binding site at the minor groove of the binaphthyl spacer. By changing the methanol content of a water‐methanol mixture, this host can be switched from an efficient binder of neutral naphthalene guests to a good host for potassium cations. The activities of the two binding sites in 7 are almost entirely independent of each other; consequently, the binding of a naphthalene guest in the 1:1:1 (host‐naphthalene‐K+) complex is nearly as strong as in the 1:1 complex. The methyl ester of (S)‐naproxen forms stable complexes with the racemic hosts 6 and 7. The 1H NMR spectra of these complexes show considerably different shifts for the aromatic resonances of the host enantiomers. These differences indicate the formation of diastereomeric complexes of different geometries or stabilities.