We describe the synthesis, the structure, and the behavior as a chiral solvating agent of the enantiomers of α, α′-bis (trifluoromethyl)-10, 10′-(9, 9′-biantryl) dimethanol. The thermodynamics of several associations are presented. We conclude that the association needs the approximation of the aromatic systems and that the geometry of complexation is the main factor that defines the enantiodiscrimination.