Contents of total and extractable heavy metals, carbonates, MnO and Fe2O3, organic matter, and matrix components such as SiO2, Al2O3, CaO, Na2O, MgO, TiO2, K2O and P2O5 are used along with principal component analysis (PCA) for studying distribution, mobility and binding behaviour of Cd, Cr, Cu, Ni and Pb in the Louro River (Galicia, Spain). Eleven surficial sediment samples were taken along the beds of the river course. Total metal concentrations were obtained after microwave-assisted digestion whilst extractable metal contents were obtained following a three-stage sequential extraction scheme (i.e. soluble, reducible and oxidisable fractions). Loading plots of heavy metals bound to carbonates, Fe-Mn oxides, organic matter and aluminosilicates allowed determination of binding behaviour. Correlations found indicate that Pb and Cu are mainly discharged from urban wastes, whereas Cr and Ni are from electroplating and galvanizing industries. The occurrence of diffuse pollution sources along the river can account for the binding behaviour of Cd. Metal mobility decreased in the order: Cd > Pb > Cu > Ni > Cr. Despite total contents indicating moderate-to-high heavy metal pollution in this river, metals are mostly distributed in the residual fraction, hence showing a low risk of mobility.