The conformational diversity of the (3R,4S,8R,9R)-9-[(3,5-bis(trifluoromethyl)phenyl))-thiourea](9-deoxy)-epi-cinchonine organocatalyst is discussed. Low-temperature NMR experiments confirmed a self-association process, which promotes the quinoline rotation between two intramolecularly hydrogen-bonded monomeric conformers of the catalyst. The balanced population of the coexisting monomeric and dimeric species allowed us to conduct a structural study of a rather complex conformational dynamics of the pure catalyst. The study is extended by a comparison with other members of the bifunctional amine-thiourea organocatalyst family. Changes in the molecular structure of the catalysts influence the interplay between intra- and intermolecular hydrogen bonding, and yield different extent of catalyst self-association. By assessing the conformation of the individual states, we established the thermodynamic model of a self-association promoted conformational transition. Copyright © 2009 John Wiley & Sons, Ltd.