N-Alkyl ammonium resorcinarene chlorides are stabilized by an intricate array of intra- and intermolecular hydrogen bonds that leads to cavitand-like structures. Depending on the upper-rim substituents, self-inclusion was observed in solution and in the solid state. The self-inclusion can be disrupted at higher temperatures, whereas in the presence of small guests the self-included dimers spontaneously reorganize to 1:1 host–guest complexes. These host compounds show an interesting ability to bind a series of N-alkyl acetamide guests through intermolecular hydrogen bonds involving the carbonyl oxygen (C[DOUBLE BOND]O) atoms and the amide (NH) groups of the guests, the chloride anions (Cl−) and ammonium (NH2+) cations of the hosts, and also through CH⋅⋅⋅π interactions between the hosts and guests. The self-included and host–guest complexes were studied by single-crystal X-ray diffraction, NMR titration, and mass spectrometry.