Both derivatization of free captopril in human plasma samples using monobromobimane as fluorescent label and the corresponding HPLC-fluorescence detection (FLD) method were validated. Calibration curve for the fluorescent captopril derivative in plasma samples is linear in the ppb-ppm range with a detection limit of 4 ppb and an identification limit of 10 ppb (P%: 90; nu > or = 5). These methods were successfully applied on bioequivalence studies carried out on some marketed pharmaceutical formulations.