A detailed study on the effect of the buffer concentration and the magnitude of the superimposed hydrodynamic flow on separation performance in CZE with contactless conductivity detection was carried out with capillaries of 10, 25, and 50 m internal diameter. It was confirmed that capillaries of narrow internal diameters require higher buffer concentrations for best sensitivities. For all diameters it was found that electrodispersion was the most pronounced band-broadening factor for relatively long residence times. For shorter times, Joule heating related band broadening appears to be the most significant factor, which means that best separation efficiencies are obtained with the narrowest capillaries. As detection limits are as good for capillaries of 10 m internal diameters as for the other diameters when using contactless conductivity detection, these narrow capillaries are, therefore, generally of benefit when employing this detection technique. Hydrodyamic flow was found to have only a very limited effect on band broadening; an effect was only noticeable for the 50 m capillary and relatively high flow rates.