A novel flow injection system incorporating a micro-column packed with carbon nanotubes (CNTs) as an adsorbent has been applied to the on-line preconcentration of trace silver with detection by flame atomic absorption spectrometry. Silver is first chelated by dithizone (H2Dz), then retained on the CNTs surface and afterward quantitatively eluted by methanol. Influencing parameters, including the concentration of reaction reagent, enrichment variables, and elution variables were investigated. The adsorption mechanisms of Ag-H2Dz chelate retained onto the CNTs surface have also been studied. By loading 6.9 mL sample solution, a linear calibration graph is obtained within the range of 3–120 µg L−1with R of 0.9996, and a detection limit (3σ) of 0.8 µg L−1is achieved, along with a precision of 1.6% R.S.D. at the 30 µg L−1level (n = 7). The dynamic sorption capacity of CNTs for silver is 122 mg g−1. The procedure is demonstrated by measurement of spike recovery in a series of water samples, giving rise to spike recoveries in the range of 96.8–99.7%. [ABSTRACT FROM AUTHOR]