We have studied the distribution and sorption behavior of phosphate and arsenate in bed-sediments of the Anllóns river (NW Spain). As a consequence of the intense gold-mining activity in the past, substantial amounts of arsenic were found in the river sediments. For phosphorus, higher concentrations were found near two sources of P pollution. Sorption isotherms were described by the Freundlich, Langmuir and Tempkin equations. In general, the sediments sorbed more P than As. The equilibrium P concentration (EPC) reveals that sediments act as a scavenger for soluble P; by contrast, equilibrium As concentration (EAC) values were high for the As-rich sediments and correlates well with total arsenic content. Amorphous Fe oxides content, organic matter and fraction of clay plus silt were the main properties of the sediments related with the sorption of arsenate and phosphate. The results obtained provide a first estimate of the sorption behavior and availability of the phosphate and arsenate anions in the sediments of the Anllóns river.