A fast and reliable dispersive liquid–liquid microextraction (DLLME) method for the determination of trace levels of silver by flame atomic absorption spectrometry (FAAS) was developed. The method is based on highly-efficient separation and preconcentration of silver by the complex formation of Ag(I) with 2-mercaptobenzimidazole and extracted by DLLME procedure using carbon tetrachloride as extraction and acetone as disperser solvent. After establishment of a cloudy solution, the phase separation is achieved and Ag(I) is determined in the enriched phase by FAAS. The method yields a linear calibration curve in the concentration range of 1–100ngmL −1 of Ag(I), and the limit of detection is 0.41ngmL −1 . The proposed method was successfully applied to determine the trace amounts of silver in water, radiology film processing wastewater and ore samples.