Hyperbranched amine-modified capillary columns containing multiple terminal amine functional groups were prepared by repeating simple reactions of amine and diglycidyl. The retention behavior of some common inorganic anion samples (i.e. -) on the prepared columns was investigated by ion chromatography, and was then compared to the retention behavior using stationary phases reacted with other amines. The eluents contained sodium chloride in neutral eluent conditions, and sodium chloride and hydrochloric acid in acidic conditions were used as the mobile phases. The retention times of inorganic anions and hydrophobic samples increased with increasing generation of hyperbranched stationary phases. In addition, the anion-exchange capacities were determined by breakthrough curves.