The aim of this study was to integrate hydrochemical and sediment data in order to obtain a picture of the pollution state of the Tagus River along central Spain. This area is of special interest because tributaries from the Madrid region are discharged and no previous data were available. Waters and sediments were sampled between 2002 and 2004 from selected sites before and after Jarama River confluence (Madrid city input). The samples were analysed for more than 50 parameters, including those of physico-chemical nature and those reporting the pollution caused by both metals and organic compounds. The quality of waters for different uses has been tested and statistical quality indexes of both global and partial type has also been established. Sediments pollution state was evaluated by comparison with general quality standards. A high degree of pollution and general degradation was observed in the Tagus River downstream the Jarama River input. The pollution of waters is mainly related to parameters indicators of organic pollution from urban sewage. In sediments, a dramatic increase in the concentration of trace metals was found in different points, exceeding toxicological threshold. Further studies would be necessary for organic pollutants and also to evaluate the remobilization potential.