A method based on reversed-phase high-performance liquid chromatography (RP-HPLC) with amperometric detection with a glassy carbon electrode at a constant potential of 1.4 V is reported for the separation and identification of aflatoxins B₁, B₂, G₁ and G₂ in a model mixture. The chromatography was performed on a PAH-Baker column with a ternary mobile phase containing methanol, acetonitrile and aqueous LiClO₄ electrolyte. Aflatoxin G₁ showed the highest electroactivity in the compound series studied. Calibration curves of aflatoxins G₁ and B₂ were linear up to 0.2 and 0.3 mmol/l, respectively. Sensitivity varied between 7 and 10 ng for the different aflatoxins. The combination of different HPLC detectors in the analysis of these compounds was applied to investigate the stability of aflatoxins G₁ and B₂.