Flow systems for precise and accurate coulometric determinations of ions that were developed on the basis of electrolytic ion transfer at the aqueous|organic solution (W|O) interface are reviewed. The electrolysis cell in the system is composed of a porous poly(tetrafluoroethylene) tube (1.0 mm inner diameter), a metal wire (0.8 mm diameter) inserted into the tube, O into which the tube is immersed, a reference electrode in O and a platinum wire counter electrode in O. The electrolysis is carried out by forcing W containing a species of interest to flow through the narrow gap between the tube and the metal wire. The coulometric determination can be performed with an efficiency of more than 99% and a precision of better than 0.2% based on the ion transfer under an optimum condition, even if the ion is redox inert such as Na(+), K(+), Mg(2+), Ca(2+), ClO(4)(-), picrate or alkylsulfonates. The system can be applied to selective electrolytic solvent extraction of ions.