Fused silica columns of 4.6 μm i.d. were coated with 3-sulfopropylsilane as a cation exchanger and 3-(2-aminoethyl-amino)-propylsilane as an anion exchanger. Fast separations of cations (< 25 seconds) and of anions (< 35 seconds) were obtained, using a potentiometric microelectrode as a detector. In proceeding towards smaller i.d.s, a mixture of alkali metal cations could be separated successfully in an uncoated fused silica capillary of 2.3 μm i.d. as a result of retention by the surface silanol groups at pH 9.4.