The reactions of tris(p-tolyl)antimony, tris(3-fluorophenyl)antimony, and tris(4-fluorophenyl)antimony with 2-hydroxybenzaldoxime at equimolar amounts in diethyl ether in the presence of hydrogen peroxide have been studied. It has been established that 2-hydroxybenzaldoxime reacts as a bifunctional compound, and the simultaneous oxidation and dearylation of triarylantimony is observed. The products of these reactions are bis(μ3-2-oxybenzaldoximato-O, O′, N)-(μ2-oxo)-tetrakis(p-tolyl)-diantimony (I), -tetrakis(3-fluorophenyl)diantimony (II), and -tetrakis(4-fluorophenyl)diantimony (III), in which two structurally equivalent antimony atoms linked via two tridentate bridging ligands and an oxygen atom have a distorted octahedral coordination with the C2O3N surrounding according to X-ray diffraction study data. Their molecules have three types of Sb–O distances with the bridging oxygen atom (1.942(5), 1.946(5) Å in IA and IB, respectively, 1.948(3), 1.953(2) Å in II, and 1.954(3), 1.958(3) Å in III), the oxygen atoms of oxime groups (2.087(7) Å in IA and IB, 2.076(2), 2.097(2) Å in II, and 2.094(3), 2.081(3) Å in III), and the oxygen atoms of hydroxy groups (2.022(7), 2.024(7) Å in IA and IB, respectively, 2.002(3), 2.010(3) Å in II, and 2.015(4), 2.019(3) Å in III) and Sb⋯N coordination bonds (2.236(8), 2.238(9) Å in IA and IB, respectively, 2.256(3), 2.230(3) Å in II, and 2.266(4), 2.251(4) Å in III).