In the present work, a novel, simple, and efficient method for the determination of silver in natural water samples was developed. The method is based on the extraction of silver with coacervate made up of decanoic acid reverse micelles and the subsequent determination by flame atomic absorption spectrometry (FAAS). Dithizone was used as a chelating agent. To obtain the best extraction results, some experimental parameters (such as coacervate composition, pH, concentration of chelating agent, and ionic strength) affecting the extraction efficiency were investigated and optimized. Under optimum conditions, the calibration curve was linear in the concentration range of 5-200 µg L -1 , with the correlation coefficient (r) equal to 0.995. The limit of detection and the enrichment factor were 1.6 µg L -1 and 15, respectively. The method was successfully applied to the analysis of silver in natural water samples.