Triarylphosphanes 1 (Ar3P; Ar = Ph, 4-MeC6H4), triphenylarsane (2), and triarylstibanes 3 (Ar3Sb; Ar = 2-MeC6H4, 2-MeOC6H4) reacted with trifluoromethanesulfonamide (7a) in the presence of equimolar diethyl azodicarboxylate to afford the corresponding triaryl(sulfonylimino)pnictoranes [Ar3M=NSO2CF3; 8 (M = P), 9 (M = As), 10 (M = Sb)]. The Kirsanov-type reaction of triarylantimony dichlorides 5 (Ar3SbCl2; Ar = 2-Mec(6)H(4), 2-MeOC6H4) and triarylbismuth dichlorides 6 (Ar3BiCl2; Ar = 2-MeC6H4, 2-MeOC6H4, 2,4,6-Me3C6H2) with sulfonamides 7 (H2NSO2R; R = CF3, 4-MeC6H4, Me) in the presence of 2 equiv of potassium text-butoxide yielded triaryl(sulfonylimino)-lambda(5)-stibanes 10 and -bismuthanes 11, respectively, The ortho-substitution in aryl ligands of 10 and 11 has been found to bring about considerable kinetic stabilization of the reactive Sb=N and Bi=N bonds. A structural comparison was made for a series of triaryi(sulfonylimino)pnictoranes 8-11 by IR spectroscopy and X-ray crystallography. In the IR spectra of 9-11, SO2 asymmetric stretching absorptions (v(SO2)) were observed at lower wavenumbers as compared to those of phosphorus counterparts 8. The difference in frequency (Deltav(SO2)) from 8 increased progressively as the pnictogen element being utilized moved down the group 15 column on the periodic table. X-ray crystallographic analyses of eight of the triaryl(sulfonylimino)pnictoranes prepared confirmed the increasing single-bond character of the M=N bond, with the contribution from the canonical structure M+-N=S(O)-O-increasing in importance in the order P < As < Sb < Bi. Among all triaryl(sulfonylimino)pnictoranes examined, only imino-lambda(5)-bismuthanes 11 oxidized alcohols to carbonyl compounds.