Potentially hexadentate phosphoryl podands 1,2-bis[2-((2-diphenylphosphorylmethyl)phenoxy) ethoxy]cyclohexane (L), 1,2-bis[2-((2-diphenylphosphoryl)phenoxy)ethoxy]cyclohexane (L1), and 1,2-bis[2-((2-diphenylphosphorylmethyl)phenoxy)ethoxy]benzene (L2) are synthesized. Stability constants of complexes formed by L, L1, and L2 with alkali-metal 2,4-dinitrophenolates in mixed THF—CHCl3 solutions (4: 1 by volume) are determined. Electroanalytical characteristics of ion-selective electrodes with hexadentate phosphoryl podands having different structures used as active components of their plasticized membranes are compared for cations of alkali and alkaline-earth metals. The IR spectra are described. The crystal structure of L is studied by X-ray diffraction.