Retention behavior of C1–C6 aliphatic monoamines (methylamine, ethylamine, propylamine, butylamine, amylamine and hexylamine) on columns (150mm×6mm i.d.) packed with various anion-exchange resins (styrene–divinylbenzene (PS–DVB) copolymer-based strongly basic anion-exchange resin: TSKgel SAX, polymethacrylate-based strongly basic anion-exchange resin: TSKgel SuperQ-5PW and polymethacrylate-based weakly basic anion-exchange resin: TSKgel DEAE-5PW) and unfunctionized polymethacrylate resins (TSKgel G5000PW and TSKgel G3000PWXL) was investigated with basic solutions (sodium hydroxide and heptylamine) as the eluents. Due to strongly electrostatic repulsion (ion-exclusion effect) between these anion-exchange resins and these amines, peak resolution between these amines on these anion-exchange resin columns was unsatisfactory with both sodium hydroxide and heptylamine as the eluents. In contrast, these polymethacrylate resins were successfully applied as the stationary phases for the separation of these C1–C6 amines with heptylamine as eluent, because of both small hydrophobicity and small cation-exchange ability of these resins. Excellent simultaneous separation, highly sensitive conductimetric detection and symmetrical peaks for these C1–C6 amines were achieved on the TSKgel G3000PWXL column in 35 min with 5 mM heptylamine at pH 11.1 as the eluent.