An end-column electrical decoupler contructed with perfluorosulfonated ionomer (Nafion) is described. This decoupler was fabricated at the cathodic end of the separation capillary by casting liquid Nafion ion exchange powder over a copper-plated tungsten wire. The internal diameter of the flow channel was controlled by adjusting the thickness of the copper plating. This design overcomes problems of conventional end-column detection such as low sensitivity due to low collection efficiency of analytes at the detection electrode, difficulty in precise placement of the detection electrode, and the need to use small-bore capillaries (<-25 micron). The loss of cationic analytes observed with long-cast Nafion on-column decouplers was significantly reduced. The high current shunting capability of the long Nafion decoupler was maintained in this configuration. Elimination of the detection capillary required for on-column electrical decouplers provided higher separation efficiency by maintaining plug-type flow throughout the system. Four model catecholamines were well separated within 5 min with separation efficiency of up to 230 000 plates and migration time reproducibilities of <0.6% RSD. With the optimized experimental conditions, detection limits of 3 nM for the catecholamines were achieved in a Ringer's solution matrix (to model a microdialysis sample).