Records on pollution by metals of minor economic importance (e.g. silver and thallium) but which prove to be toxic are rarely documented in river sediment. This study used two sediment cores collected downstream of the Seine River to describe the temporal evolution of Ag and Tl concentrations in an urban catchment. Radionuclide analysis (i.e. Cs-137 and Pb-210) allowed dating sediment deposition within the cores (1933-2003). Ag concentration reached maximum values of 14.3-24.6 mg kg-1 in the 1960s and 1970s, before gradually decreasing up to values which approximated 4 mg kg-1 in 2003. In contrast, Tl concentrations remained roughly constant throughout the core (median value of 0.86 mg kg-1). Suspended solids was collected at upstream locations in the catchment to derive the background concentrations in Ag and Tl. Very high Ag concentrations were measured in the upstream Seine River sites (0.33-0.59 mg kg-1), compared to the values reported in the literature (0.055 mg kg-1). This suggests the presence of a widespread and ancient Ag pollution in the Seine River basin, as demonstrated by the very high Ag enrichment ratios recorded in the cores. Annual flux of particulate Ag in the Seine River was estimated at 1.7 t yr-1 in 2003. In contrast, Tl concentrations remained in the same order of magnitude as the natural background signal (0.3-0.5 mg kg-1). This study suggests that the Seine River basin is free of Tl contamination. Future concerns should hence mostly rely on Ag contamination, in a context of increasing Ag uses and possible releases to the environment.