Within the bioticl ligand model, which describes relationships between chemical speciation and metal binding at an organism's surface, multicomponent (long-term) metal uptake by plants has seldom been studied. In the present work, we exposed perennial ryegrass to nutrient solutions with two levels of Cd, Cu, Ni, Pb, and Zn (1 and 0.1 μM) and with or without 30 mg/L of humic acid. Iron and Mn concentrations were constant over all treatments. The hypothesis tested was that humic acid lowers the free and labile metal concentration and, therefore, reduces the metal uptake and, finally, the metal content of the plant. The free metal ion concentrations in the nutrient solutions were measured by the Donnan membrane technique and labile metal concentrations by diffusive gradients in thin-films. The metal content of the shoots depends on the metal content of the roots. The metal content of the roots is a function of the adsorption of metals on the root surface. In a multicomponent system at metal concentrations of 1 μM, humic acid decreased Cu, Pb, and Fe adsorption at the root surface, but it increased Cd, Zn, and Mn adsorption at the root surface. Complexation of cations such as Cu, Pb, and Fe with high affinity for (dissolved) organic matter may lead to increased uptake of cations with low affinity for organic matter (Ni, Zn, and Cd) because of competition between cations at the root surface. The results suggest that competition between metal ions can play a major role in multicomponent metal uptake, which has to be taken into account during risk assessments of metal-polluted soils.