A novel class of resorcinarene-based cavitands 2a−e that fold into a deep (8 × 10 A dimensions) open-ended cavity by means of intramolecular hydrogen bonds has been synthesized. As follows from the FTIR and 1H NMR spectral data in apolar solvent, a seam of eight intramolecular hydrogen bonds is stitched along the upper rim of the structure 2a−e; the amide CO...H−N interactions bridge adjacent ringsinterannular bindingand are held in place by the seven-membered intraannular hydrogen bonds. The self-folding in 2a−e is reversibly controlled by solvent and temperature. Complexation of self-folding cavitands 2a−e with organic molecules such as (1-substituted) adamantanes, lactams, and cyclohexane derivatives was demonstrated by 1H NMR spectroscopy in CDCl3, benzene-d6 and p-xylene-d10; the binding energy -ΔG° values of 2−4 kcal mol-1 in p-xylene-d10 at 295 K were calculated. The exchange between complexed and free guest species is slow on the NMR time-scale, and it is proposed that hydrogen bonds are responsib...