A rapid and simple quantitative method for the simultaneous determination of the four aflatoxins (AFs) B1, B2, G1 and G2 was developed using reverse homogeneous liquid–liquid extraction (RHLEE) and HPLC post-column derivatization-fluorescence (HPLC-FL) detection. The method based on the rapid extraction of AFs from a methanolic sample into chloroform after addition of water containing KBr, with a method we called reverse homogeneous liquid–liquid extraction. Recoveries were in the range of 88–125% and the limits of detection were between 0.001–0.042 ng g−1 for different AFs. Wheat and pistachio were chosen for the analysis of real samples and the method was also successfully applied to a FAPAS® TEST MATERIAL (T04151).