(Chemical Equation Presented) The 400 MHz 1H NMR spectrum of the tetramethoxycalixarene 2 (possessing hydroxyl groups at the bridges) in commercial acetone-d6 displays five signals (an isotopic multiplet) for a pair of methoxy groups. Inspection of the X-ray structures of 2 and its isomer 3 indicates that in the adopted 1,3-alternate conformation, the methoxy groups intramolecularly hydrogen bonded to neighboring OH groups are oriented "in" (pointing toward the cavity). Upon dissolution of 2 in acetone-d6, none, some, or all of the OH protons exchange with the deuterium atoms present in the residual water of the solvent. Several species (mutually relating as isotopomers and isotopologues) differing in the number and positions of the deuterated hydroxyl groups are possible for 2. In three of these species, the "in"-"out"/"out"-"in" conformational equilibrium of a pair of methoxy groups is nondegenerate. The four external lines of the apparent multiplet are ascribed to a single- and double-isotopic perturbation of the "in"-"out" conformational equilibrium of a pair of methoxy groups. On the basis of the assignment of the signals to the individual species and their statistical distribution, the intensities of the components of the isotopic multiplet obtained at different isotopic enrichments of the hydroxyl groups could be simulated. A sample of 2 55% deuterated at the hydroxyl groups in CDCl 3 displayed an isotopic multiplet consisting of nine signals. The isotopic multiplet observed for the OH groups of 2 in acetone-d6 was simulated at different deuteration enrichments.