A contactless conductivity detector (C 4 D) performance has been tested on a simple capillary electrophoretic separation in a standard fused-silica capillary with an external diameter of 360 mm and in a thin-walled capillary (an external diameter of 150 mm); the internal diameters of the two capillaries were identical, equal to 75 mm. Potassium and sodium ions have been separated in a morpholinoethanesulfonic acid/histidine background electrolyte (MES/His), over a wide range of its concentrations (0 -100 mM). At low MES/His concentrations, the C 4 D response, obtained from the height of the potassium peak, is by 100 to 200 per cent higher for the thin-walled capillary and the calibration dependences are linear, in contrast to the thick-walled capillary. These differences between the two capillaries decrease with increasing MES/His concentration, the C 4 D response in the thin-walled capillary is then higher by mere 20 per cent and the calibration dependences are linear in both the capillaries. The highest sensitivities have been obtained at a MES/His concentration of 50 mM, with LOD values for potassium ion of 2.0 and 2.6 mM, in the thin-and thick-walled capillaries, respectively. The signal-to-noise ratios and the plate counts are generally similar for the two capillaries. It follows from the results that special thin-walled capillaries can be advantageous when background electrolytes with very low conductivities must be employed.