A simple, rapid and dispersive liquid–liquid microextraction-solidification of floating organic drop procedure was combined with ﬂame atomic absorption spectrometry and established for the determination of trace amounts of silver. 5-(4-dimethylamino-benzylidine) (Rhodenylene) ligand and 1-dodecanol were used as complexing agents and extracting solvents, respectively. The optimum extraction efficiency of silver was obtained after optimization of the pH, concentration of ligand, the nature and amount of solvent extraction, salt increase effect, extraction time, extraction temperature and stirring rate. The effects of various ions on the recovery of Ag were also investigated. The limit of detection defined as 3SB/m was 1.55 ngL−1. The sensitivity for three eight measurements of 10 and 100 μgL−1 of silver was 1.55 ngL−1. The relative standard deviation (RSD) for the measurements of 0.20 μgL−1 of silver was ±2.3%. Water well, mineral water and urban drinking water samples were analyzed for Ag amount. The microextraction method was satisfactorily used for the determination of Ag in various environmental waters.