The feasibility of using capillary electrophoresis (CE) with a new electrolyte system for the analysis of alkali metal, alkaline-earth metal cations and ammonium in atmospheric aerosols has been demonstrated. 1,1'-Di-n-heptyl-4,4'-bipyridinium (DHPB) hydroxide was used as the UV-absorbing species, which allowed for the indirect UV detection of cations at 280 nm, while glycine, 18-crown-6 ether and methanol were employed to improve the separation of the studied cations. The precision of migration time and peak area was better than 0.2% and 5%, respectively. Separation efficiencies were between 90 000 and 600 000 theoretical plates per meter, and detection Limits between 9 and 60 ng/ml. With the described electrolyte composition it is also possible to determine manganese and cadmium, and short-chain aliphatic amines. The comparison of CE results with ion chromatography obtained for cations in atmospheric aerosols is presented.