Anion selectivities of poly(vinylchloride) (PVC) plasticized membranes containing uranyl salophene derivatives were presented. The influence of the membrane components (i.e. ionophore structure, dielectric constant and structure of plasticizer, the amount of incorporated ammonium salt) on its phosphate selectivity was investigated. The highest selectivity for H2PO4− over other anions tested was obtained for lipophilic uranyl salophene III (without ortho-substituents) in PVC/o-nitrophenyl octylether (o-NPOE) membrane containing 20 mol% of tetradecylammonium bromide (TDAB). Ion-selective electrodes (ISEs) based on these membranes exhibited linear response in the range 1–4 of pH2PO4− with a slope of 59 mV/decade. The introduction of ortho-methoxy substituents in ionophore structure decreased the phosphate selectivity of potentiometric sensors.