The crystal structure of 1:1 inclusion complex of hexyltrimethylammonium bromide (6TAB) and rac-1, 1'-bi-2-naphthol (BNP) was analysed by the X-ray diffraction method. It was shown that the bromide anion participates in a hydrogen bund with one of the OH groups of BNP (Ol ... Br, 3.22(1)Angstrom). The bromide anion also plays a role as the hydrogen acceptor of me OH group of the water molecule (OW ... Br, 3.21(3)Angstrom). A strong hydrogen bond was found between the other OH group of BNP and oxygen of the water molecule (O2 ... OW, 2.63(3)Angstrom). The short C-HC distances between hydrogen atoms of the alkyl chain together with the methyl groups and carbon atoms of the aromatic rings suggested C-H ...pi interactions. The atomic distances shorter than the sum of the van der Waals radius (2.97 Angstrom) were C10 ... H6 2.85 Angstrom, C14 ... H9 2.83 Angstrom, and C16 ... H11 2.88 Angstrom. The X-ray powder diffraction studies on the complex suggested that the complex crystals can be obtained by crystallization from the solution and also by mixing powdered samples in a mortar.