The combined use of chemometrics and chemiluminescence (CL) measurements,with the aid of the stoppedflow mixing technique,developed a simple time-resolved CL method for the simultaneous determination of captopril (CPL) and hydrochlorothiazide (HCT).The stopped-flow technique in a continuous-flow system was employed in this work in order to emphasize the kinetic differences between the two analytes in cerium (Ⅳ)-rhodamine 6G CL system.After the flow was stopped,an initial rise of CL signal was observed for HCT standards,while a direct decay of CL signal was obtained for CPL standards.The mixed CL signal was monitored and recorded on the whole process of continuousflow/stopped-flow,and the obtained data were processed by the chemometric approach of artificial neural network.The relative prediction error (RPE) of CPL and HCT was 5.9% and 8.7%,respectively.The recoveries of CPL and HCT in tablets were found to fall in the range between 95% and 106%.The proposed method was successfully applied to the simultaneous determination of CPL and HCT in a compound pharmaceutical formulation.