Tri( o -tolyl) antimony dioximates were synthesized by the reaction of tri( o -tolyl) antimony with 5-nitrofurfural and thiophen-2-carbaldehyde oximes in ether in the presence of hydrogen peroxide or tert -butylhydroperoxide (1: 2: 1 mol). Antimony atoms in the reaction products have distorted trigonal-bipyramidal coordination with the intramolecular distances Sb···N shorter than the sum of the van der Waals radii of Sb and N by ~1 Å.