A simple and fast flow method for the trace level determination of p-toluidine, 2-methyl-5-nitroaniline, and 2,4-dinitroaniline in aqueous samples is reported. These amino/nitroaromatics are related to trinitrotoluene (TNT) and appear during the degradation process of the explosive. The chemical principles of ion-pair formation and liquid-liquid extraction are applied: In aqueous acidic medium, the protonated analyte [HA]+ makes an ion-pair with the tetrachloroaurate(III) ion, followed by on-line ion-pair extraction into the dichloromethane carrier used. After membrane separation, the CH2Cl2 containing the ion-pair, [HA]+[AuCl4]−, is mixed with the reversed micellar luminescent reagent of luminol (in 0.3 M Na2CO3) prepared from cetyl-trimethylammonium chloride in CH2Cl2-cyclohexane and the [AuCl4−-luminol chemiluminescence (CL) output is recorded. The detection limits (S/N> 3) are: p-toluidine, 1.0 × 10−4M; 2-methyl-5-nitroaniline, 1.0 × 10−7 M; 2,4-dinitroaniline, 1.0 × 10−7 M, while the calibration curves are linear between 1.0 × 10−4 — 1.0 × 10−2 M for all the compounds. Although spectral studies indicated the formation and extraction of a very small amount of the ion-pair species, the reversed micellar-mediated CL detection system provides an alternative procedure for the determination of degradation products of the explosive TNT in environmental aqueous samples.