The reactions of pentaarylantimony with antimony derivatives Ar3SbX2 (Ar = Ph or p-Tol and X = OC(O)C6F5 or NO3) afford tetraphenylantimony pentafluorobenzoate (Ph4SbOC(O)C6F5) and tetra-p-tolylantimony nitrate (p-Tol(4)SbONO(2)). The compounds obtained were structurally characterized by X-ray diffraction analysis. The Sb atom in Ph4SbOC(O)C,FS has a distorted trigonal-bipyramidal environment with an axial perfluorobenzoate group. The trigonal-bipyramidal coordination of antimony in p-Tol(4)SbONO(2) is strongly distorted, with the O atom of the nitrato group lying in the axial plane.