The interaction of triarylantimony (Ar = 4-FC6H4, 3-MeC6H4, 3-FC6H4) with tert-butyl hydroperoxide and 3,4-dimethylbenzenesulfonic acid, as well as 2,4-dinitrobenzenesulfonic and trifluoromethanesulfonic acids (1:2:1, 1:1:1, and 3:2:3 mol) in diethyl ether has led to synthesis of triarylantimony di- and oxo-sulfonates: tris(4-fluorophenyl)antimony bis(2,4-dimethylbenzenesulfonate) (4-FC6H4)3Sb(OSO2C6H3Me2-2,4)2 (1), tris-(3-methylphenyl) anti-mony µ-oxo-bis-(2,4-dinitrobenzenesulfonate) [(3-MeC6H4)3Sb(OSO2C6H3NO2-2,4)]2O (2), and a solvate of nona-(3-fluorophenyl)tristiboxane-1,5-diyl bis-(trifluoromethanesulfonate) with benzene CF3OSO2Sb(3-FC6H4)3OSb(3-FC6H4)3OSb(3-FC6H4)3OSO2CF3·PhH (3), which have been structurally characterized. The X-ray diffraction pattern has been obtained at 293 K on an auto-matic diffractometer D8 Quest Bruker (MoKα-radiation, λ = 0.71073 Å, graphite monochromator): crystals 1 [C34H30O6S2SbF3, M 777,45; the monoclinic syngony, the C2/c symmetry group; cell parameters: a = 18.980(10), b = 15.667(8), c = 12.271(7) Å; α = 90.00, β = 114.36(2), γ = 90.00; V = 3324(3) Å3; the crystal size is 0.51 × 0.32 × 0.82 mm; intervals of reflection in-dexes are –29 ≤ h ≤ 33, –27 ≤ k ≤ 27, –21 ≤ l ≤ 21; total reflections 63539; independent reflec-tions 9421; Rint 0.0468; GOOF 1.011; R1 = 0.0400, wR2 = 0.0801; residual electron density 0.88/0.92 e/Å3], 2 [C54H48N4O15S2Sb2, M 1300.58; the triclinic syngony, the P–1 symmetry group; cell parameters: a = 10.332(5), b = 12.312(5), c = 13.045(4) Å; α = 77.744(12), β = 84.85(2), γ = 74.25(2); V = 1559.8(11) Å3; the crystal size is 0.37 × 0.19 × 0.16 mm; inter-vals of reflection indexes are 15 ≤ h ≤ 15, 18 ≤ k ≤ 18, 19 ≤ l ≤ 19; total reflections 75043; independent reflections 11314; Rint 0.0372; GOOF 1.093; R1 = 0.0506, wR2 = 0.1511; residual electron density 2.75/0.59 e/Å3], and 3 [C62H42O8F15S2Sb3, M 1629.33; the monoclinic syngony, the P21/n symmetry group; cell parameters: a = 15.933(12), b = 16.759(12), c = 24.13(2) Å; α = 90.00, β = 91.51(3), γ = 91.51(3); V = 6441(9) Å3; the crystal size is 0.47 × 0.2 × 0.18 mm; intervals of reflection indexes are 20 ≤ h ≤ 20, 21 ≤ k ≤ 21, 31 ≤ l ≤ 31; total reflec-tions 139052; independent reflections 14671; Rint 0.0444; GOOF 1.134; R1 = 0.0435, wR2 = 0.0998; residual electron density 1.38/1.12 e/Å3], the antimony atoms have a distorted trigonal-bipyramidal coordination with the oxygen atoms in axial positions (trans-OSbO и cis-OSbС angles are 177.94(6)°, 85.02(6)–93.75(6)° (1), 175.52(6)°, 81.11(11)–94.47(9)° (2), and 175.09(14)178.32(13)°, 80.60(17)–96.79(17)° (3). The Sb–Osulf. bond lengths are 2.1212(17) Å (1), 2.289(2) Å (2), and 2.402(4), 2.430(4) Å (3), they are longer than those for Sb–Obridge 1.9340(7) (2) and 1.915(3)–2.039(3) Å (3). The SbC bond lengths in 1–3 change in a narrow range of values: 2.086(2)2.0946(19), 2.104(3)2.108(3), and 2.094(5)2.124(4) Å, respectively. The structural organization in crystals 1–3 is caused by the weak van-der-Waals interactions: S=О···Н–C 2.46–2.62 Å (1), S=О···Н–C 2.39–2.65 Å (2), and S=О···Н–C 2.46–2.65, C–F···Н–C 2.46–2.55 Å (3). Complete tables of coordinates of atoms, bond lengths and valence angles for structures 13 are deposited at the Cambridge Structural Data Bank (No. 1919945, 1898995 and 1575647; deposit@ccdc.cam.ac.uk; http: //www.ccdc.cam.ac.uk).