The structure of the DMSO (dimethyl sulfoxide) solvate of the macrocyclic [22] dimer, 17,17,37,37‐tetramethyl‐2,12,22,32‐tetraoxa‐7,27‐dithianonacyclo[36.2.2.2.‐2.2.2.2.2.2]hexapentaconta‐3,5,8,‐10,13,15,18,20,23,25,28,30,33,35,38,40,41,43,45,47,49,51,53,55‐tetracosaene 7,7,27,27‐tetraoxide, formed from ‐dichlorodiphenyl sulfone and bisphenol‐A has been determined by single‐crystal techniques and the structure of the unsolvated dimer refined using X‐ray powder diffraction data. The molecular conformations are similar and phenyl–phenyl stacking interactions are apparently important in determining the molecular conformation in the solid state. . (1) cyclo‐[.: molecular weight 963.2, monoclinic, (2), (3), (2) Å, , (7) Å. (2), cyclo‐[(: molecular weight 885.06, monoclinic, , (15), (18), (12) Å, , (5) Å.