Abstract A new method has been proposed to sensitive detection of captopril based on surface plasmon resonance band of silver nanoparticles (AgNPs). The stable and well-dispersed AgNPs with strong plasmon resonance signal were synthesized in situ using a simple and rapid procedure by applying ascorbic acid as reducer and sodium dodecyl sulfate as stabilizer, at room temperature. It was found that, the decreasing of AgNPs plasmon absorbance is proportional to the concentration of captopril which allows the spectrophotometric sensing of this compound. The presented method is capable of determining captopril over a range of 0.20–2.75μmolL−1 with a limit of detection 0.07μmolL−1. The relative standard deviation for eight replicate measurements of 1.00 and 2.50μmolL−1 of captopril was 2.37% and 1.02%, respectively. The method was applied to the determination of captopril in pharmaceutical formulations with satisfactory results, which were in agreement with those of the official method.