Triaryl(trifluoromethylsulfonylimino)-lambda(5)-stibanes (Ar-3-Sb=NSO2CF3) were prepared by the Kirsanov-type reaction of triarylantimony dichlorides with CF3SO2- NH:! in the presence of KO-t-Bu and by the redox condensation of triarylstibines with CF3SO2NH2 in the presence of diethyl azodicarboxylate. The Sb=N bond of these monomeric iminol-lambda(5)-stibanes was found to possess moderate single-bond character owing to the resonance hybridization with the electron-withdrawing N-sulfonyl group.