Arsenic, Cd, Cu, Pb, Hg, and Zn were measured in sediments, biofilm, benthic macroinvertebrates, and fish from the Coeur d'Alene (CDA) River to characterize the pathway of metals transfer between these components. Metals enter the CDA Basin via tributaries where mining activities have occurred. In general, the ranking of food-web components from the greatest to smallest concentrations of metals was as follows: biofilm (the layer of abiotic and biotic material on rock surfaces) and sediments > invertebrates > whole fish. Elevated Pb was documented in invertebrates, and elevated Cd and Zn were documented in sediment and biofilm approximately 80 km downstream to the Spokane River. The accumulation of metals in invertebrates was dependent on functional feeding group and shredders-scrapers that feed on biofilm accumulated the largest concentrations of metals. Although the absolute concentrations of metals were the largest in biofilm and sediments, the metals have accumulated in fish approximately 50 km downstream from Kellogg, near the town of Harrison. While metals do not biomagnify between trophic levels, the metals in the CDA Basin are bioavailable and do biotransfer. Trout less than 100 mm long feed exclusively on small invertebrates, and small invertebrates accumulate greater concentrations of metals than large invertebrates. Therefore, early-lifestage fish may be exposed to a larger dose of metals than adults.