The chemiluminescent behaviour of captopril when reacted with a common oxidant, potassium permanganate in different acidic media is described, using the stopped-flow technique in a continuous-flow system. A 22 bit analogue-to-digital converter that acquires analogue signals at -10 and +10V and allows the power supply to the peristaltic pump to be interrupted is used in the time-resolved chemiluminescence manifold to ensure rapid, efficient mixing of chemiluminescent reagent and sample immediately before reaching the detector; this results in high precision and detectability, particularly with fast, short-lived emissions. The optimum chemical conditions for the chemiluminescence emission were investigated. It was found that a weak CL emission was emitted during the oxidation of this drug with potassium permanganate in acidic solution. The effect of common emission enhancers such as formic acid, formaldehyde, glutaraldehyde, acetaldehyde, quinine, fluorescein, rhodamine B and rhodamine 6G was studied. The parameters selected were 4.0molL-1 sulphuric acid, 0.25mmolL-1 permanganate and 0.75molL-1 formaldehyde. Four quantitative parameters adjustable via software settings, two of them typically kinetic parameters, such as rate of the light-development reaction and rate of the light-decay reaction, and the other conventional parameters, such as maximum emission intensity and total emission area, were used to obtain linear calibration graphs with each measurement parameter. The detection limits ranged from 0.011 to 0.026μgmL-1 and R.S.D. values (n=10) of 1.21-3.93 at a 0.50μgmL-1 and 2.01-3.41 at a 1.60μgmL-1 concentration levels were obtained. The method was satisfactorily applied to the determination of captopril in pharmaceutical preparations.