Isomeric preference between cyclic dialkoxy disulfides and thionosulfites is governed by the ring size of the heterocycle. Rings smaller than seven atoms prefer the thionosulfite connectivity, whereas larger rings or acyclic analogues favor the unbranched dialkoxy disulfide structure. Density functional calculations were employed to predict the crossover point at which both constitutional isomers are of comparable stability. Follow-up synthesis provides the previously unknown eight-membered ring dialkoxy disulfide 14 and seven-membered ring thionosulfite 15 from the same reaction. X-ray crystallography for all but one of the reaction products and complementary NMR analysis furnishes insights into both solid-state and solution conformations. A long-standing issue regarding the concerted vs catalyzed isomerization pathway between XSSX and X(2)S=S has been addressed for X = RO and shown to be acid dependent.