Abstract <p>By the reaction of equimolar amounts of tetraorganylphosphonium bromides with arenesulfonic acids in water, ionic tetraorganylphosphonium arenesulfonates [Ph₃PCH₂CH=CHCH₂PPh₃][OSO₂C₉H₃N(OH-4)(I-7)]₂ ∙ 4H₂O (<b>1</b>), [Ph₃P(CH₂)₅PPh₃] [OSO₂С₆H₄(COOH-2)][Br] (<b>2</b>) were obtained with a yield of up to 89%. The structural features of complexes <b>1</b> and <b>2</b> were established by X-ray diffraction. Crystals: <b>1</b> [C₅₈H₅₄I₂N₂O₁₂P₂S₂, <i>M</i> 1350.89; triclinic system, symmetry group <i>P</i>-1; cell parameters: <i>a</i> = 9.506(8) Å, <i>b</i> = 11.323(12) Å, <i>c</i> = 13.662(10) Å; α = 82.21(4)°, β = 89.26(2)°, γ = 72.60(4)°, <i>V</i> = 1390(2) ų, <i>Z</i> = 2; ρ_calcd = 1.614 g/cm³]; <b>2</b> [C₄₈H₄₅O₅P₂SBr, <i>M</i> 875.75; triclinic system, symmetry group <i>P</i>-1; cell parameters: <i>a</i> = 10.307(7) Å, <i>b</i> = 14.226(9) Å, <i>c</i> = 16.291(10) Å; α = 67.07(3)°, β = 83.74(3)°, γ = 74.65(3)°, <i>V</i> = 2122(2) ų, <i>Z</i> = 2; ρ_calcd = 1.371 g/cm³] consist of tetraorganylphosphonium cations and arene-sulfonate anions with a tetrahedral sulfur atom. The crystal of complex 2 also contains [Br]⁻ anions. The P–C bond lengths vary in the range 1.779(3)−1.815(4) Å. The bond angles of the CPC take values of 104.33(15)°−112.00(10)°. The S–O distances vary within the range of 1.4397(18)−1.4576(19) Å. Complete tables of atomic coordinates, bond lengths and bond angles for structures have been deposited in the Cambridge Structural Data Bank (CCDC nos. 2164291 (<b>1</b>) and 2165072 (<b>2</b>)).</p>