The current responses of a generation/collection (G/C) system based on dual micropipettes are simulated by the boundary element (BE) method, from which the collection efficiencies for various pipettes with different geometries are calculated. The influence of the shape of a dual micropipette on the collection efficiency, such as curvature and symmetry of the pipette, as well as the thickness of glassy band between generator and collector, is presented and discussed in detail. Moreover, the simulation results have been tested using the experiments of potassium and sodium ions transfers facilitated by dibenzo-18-crown-6 (DB18C6) at the water/1,2-dichloroethane (W/DCE) interface. These results demonstrate that the BE method is an efficient and useful approach for the simulation of collection efficiency of symmetric geometries of dual micropipettes operating in the G/C mode under transport conditions of diffusion control. However, there are still some problems for the cases of asymmetric dual micropipettes, which show rather large differences between the values of simulated and experimental ones. This work also indicates that such an ionic G/C technique should have advantages in applications when the dual pipettes have symmetric geometries.