Novel hydrogen-bonded supramolecules based on interactions between an acid and a base have been prepared from (R,R)-1,2-bis(1-adamantylmethylphosphinyl)ethane (1) and tetrafluoroboric acid. Both linear and cyclic structures have been observed. Recrystallization from CH2Cl2-AcOEt gave the linear supramolecule 2. The structure of 2 was confirmed by single-crystal X-ray analysis. On the other hand, cyclic dimer 3 was produced by recrystallization from CHCl3-AcOEt. The structure of 3 was estimated by electron spray ionization mass spectrometry and single crystal X-ray analysis. Significantly different enantiuselectivities were observed in asymmetric protonation reactions of these two supramolecules with silyl enolates.