Ionic organyl-triphenylphosphonium 2,4-dinitrobenzenesulfonates [Ph3PR][OSO2C6H3(NO2)2-2,4], R = CH2OMe (1), CH2CN (2), CH2CH = CHCH2PPh3 (3) are prepared by the reaction of organyl-triphenylphosphonium halides with 2,4-dinitrobenzenesulfonic acid in water and are structurally characterized. According to the XRD data, the phosphorus atoms in cations 1-3 have a distorted tetrahedral coordination, the sulfonate anions have a usual geometry with a sulfur atom in a tetrahedral environment. The lengths of P–C bonds vary within 1.742(2)-1.872(2) Å; the CPC bond angles fall within 104.92(6)-113.43(11)°. In the arenesulfonate anions of the complexes, the S–C distances are close to each other (1.743(2)-1.806(3) Å), all the S–O bonds are almost equal (1.4324(15)-1.477(2) Å). The [Ph3PCH2CH=CHCH2PPh3]+ cations of complex 3 contain second-order rotation-reflection axes passing through the centers of the C=C double bonds (point group C2h). The structures of 1, 3 contain short CAr⋯H(Ph) contacts (CH⋯π interactions) (2.829 Å (1), 2.769 Å (3)). The structures of 1-3 are mainly determined by weak intermolecular O⋯H contacts 2.30-2.61 Å (1), 2.23-2.68 Å (2), 2.35-2.69 Å (3). [ABSTRACT FROM AUTHOR]