The objective of this study was to investigate the influence of root exudation of organic acid anions on the speciation of major and trace metal cations in the rhizosphere of Lupinus albus cluster roots. Plants were grown in rhizoboxes containing repacked weakly acidic loam. Bulk soil solutions and, during the lifetime of cluster roots, rhizosphere solutions were collected using micro suction cups. During organic acid anion exudation bursts, metals in the rhizosphere of cluster roots were strongly mobilized. The concentrations of dissolved organic carbon derived from soil organic matter increased parallel to organic acid anions. Speciation calculations revealed that, during exudation, Al, Ca, Mn, and Zn in the cluster root rhizosphere were mainly bound with citrate, while Cu and Pb were always strongly bound to soil-derived dissolved organic matter. Our results indicate that cluster root exudation led on one hand to direct mobilization and complexation of metals like Al, Fe, and Zn by citrate and on the other hand to the mobilization of soil organic matter which complexes and solubilizes Cu and Pb.