The environmental distribution and anthropogenic dispersion of both antimony (Sb) and arsenic (As) have received considerable attention over recent years, although the ecological risk posed is still little understood in many ecosystems. The aim of this study was to examine and compare spatial and temporal uptake and biotransfer of the metalloids in foodwebs of the Bakers Creek - Macleay River catchment of northern NSW, which has been strongly affected by Sb and As contamination with over a century of gold (Au)-Sb mining and processing. Metalloid concentrations were measured in the water, sediment, and biota representing various trophic levels and diverse species assemblages (biofilms, algae, detritus, aquatic plants, macroinvertebrates, tadpoles, and fish) at fifteen morphologically and hydrologically different sites over four occasions in 2015. Data indicated that all stream components examined were variably enriched with both metalloids (e.g. 3.64 – 1187.82 µg L^-1 Sb and 0.10 – 64.79 µg L^-1 As in water; 58.69 -554.82 µg g^-1 Sb and 4.85 – 30.16 µg g^-1 As in detritus; 83.15 – 855.93 µg g^-1 Sb and 70.08 – 222.27 µg g^-1 As in sediment; 8.03 – 1203.35 µg g^-1 Sb and 13.38 – 255.36 µg g^-1 As in stream autotrophs; and 1.04 – 140.10 µg g^-1 Sb and 0.56 – 404.92 µg g^-1 As in heterotrophs) close to the source Bakers Creek (BC) site at all sampling occasions but this enrichment decreased substantially downstream from that site. The spatial distribution of Sb in water and sediment was strongly associated with distance from the mine, dissimilar to As, which was independent of distance. While bioaccumulation in the food webs existed and some of the greatest concentrations of Sb reported in biota were recorded, As showed greater uptake efficiency in foodweb biota. Temporal changes in metalloid sources (water, detritus, and sediment) to biota had little or no effect on Sb and As bioaccumulation in trophic groups, other than Sb in autotrophs collected from one site. Bioaccumulation of As in tissues of freshwater mussels, Corbicula sp., was greatest in body tissue, and As uptake was greater than Sb in all tissues. In contrast, the greatest Sb concentration in the mussels was found in the muscular foot tissue. Concentrations of Sb and As were elevated in plants, but sediment/soil to plant transfer was small, even though rhizosphere sediment/soil was elevated for both metalloids. Comparisons and mapping of metalloid transfer across feeding groups showed that neither trophic transference nor biomagnification of Sb or As through the food webs of the different sites occurred. Rather, there was a biodiminution of both metalloids with increasing trophic level. This is the first study with such a wide scope of sampling biota for both Sb and As and provides insight into metalloid ecosystem distribution and food web transfer. Ecotoxicological profiling of the measured concentrations on a range of aquatic organisms is the next practical step to better assess the risk associated with Sb and As co-occurence in aquatic environments.