The selective isomerization of cis-1,2-diphenylsulfonyl ethylene to trans-1,2-diphenylsulfonyl ethylene proceeded in supercritical carbon dioxide above 393 K without an addition of catalyst. The product yield increased with increasing temperature and was almost constant against carbon dioxide density. The 73% of product yield was obtained at 493 K and 10 MPa of carbon dioxide pressure for 60 min. The product yield obtained in supercritical carbon dioxide was larger than those obtained in organic solvents. The supercritical carbon dioxide was a dilute solvent compared with organic solvent, which probably reduced the suppression of the reaction by dense solvent. Further, only cis-sulfonyl ethylenes isomerized among several cis-ethylene derivatives. The sulfonyl group played an important role for the isomerization. (C) 2009 Elsevier B.V. All rights reserved.