An amperometric detector for hydrophobic ions based on a plasticized poly(vinyl) chloride (PVC) membrane incorporated in a flow-injection system was developed. A four-electrode potentiostat with ohmic drop compensation was used, while a flow-through cell incorporated the four electrodes and the membrane, which contained tetrabutylammonium tetraphenylborate. When the influence of the applied potential and of the flow-injection variables on the determination of tetrabutylammonium was studied, a linear relationship was observed between current peak height and ion concentration over a range of 5 Â 10 À6 ± 6 Â 10 À5 M tetrabutylammonium. Good repeatability and between-day reproducibility and high sample frequency were obtained. The effect of other ions was studied. Two different amperometric methods, indirect and direct, were also developed for the determination of dodecylsulfate in the concentration range 3 Â 10 À5 ± 9 Â 10 À4 M.