The structures of cocrystals of benzylidene-1,1 0 -bis-2-naphthol with methanol and ethanol have been studied by single crystal X-ray diffraction and 1 H-NMR spectroscopy. The cocrystal structures are stabilized by intra-and inter-molecular hydrogen bonds with the stoichiometry of a 1 : 1 host : guest. The competition experiment in the solid-liquid biphasic system between pair of guests revealed that methanol is preferentially enclathrated over ethanol in all mole fractions.