Conformational studies of 1,3-dihydroxy-4,4,5,5-tetramethyl-2-(pyridin-1-yl)imidazolidine (1a) and 1,3dihydroxy-4,4,5,5-tetramethyl-2-(pyridin-3-yl)imidazolidine (1b), carried out by using 1D 1 H-and 13 C-NMR and 2D HMQC, HMBC, and NOESY experiments and with the aid of theoretical calculations, indicate that the OH groups are trans to the pyridinyl substituent. Because the two 1 H-NMR signals of the Me groups are distinguishable and do not change between 290 and 380 K, it is proposed that 1a and 1b have each only one conformation in this temperature range. This behavior was not found with 1,3-dihydroxy-4,4,5,5-tetramethyl-2-(pyridin-2-yl)imidazolidine (1c) because its Me 1 H-NMR signals cross over at 300 K. Hence, more than one conformation must be present, beyond those produced by simple inversions. Theoretical calculations including temperature and solvent effects were performed to provide further information on the conformational analysis and to help to assign the NMR data. The combination of NMR measurements and quantum-chemical calculations is shown to be a very promising strategy for conformational analysis studies in solution.