Polyelectrolyte multilayers deposited on the wall of fused silica capillaries were used as stationary phases in open tubular ion chromatography. The multilayers were formed by flushing the capillaries with solutions of polyanions and polycations such as polydiallyldimethylammonium chloride and dextran sulphate. Columns with several bi-layers were constructed and used in low pressure non-suppressed open tubular ion chromatography of common inorganic anions (F(-), Cl(-), NO(3)(-)) and cations (Li(+), Na(+), NH(4)(+), K(+), Cs(+)) with contactless conductometric detection. Using sodium benzoate and tartaric acid eluents the separations were typically achieved in less than 35 min with separation efficiencies between 2000 and 9000 theoretical plates. A bi-functional column was prepared that contains both anionic and cationic functional groups and was used for simultaneous separation of anions and cations.