The current work examines the effects of model allochtonous (humic substances) and autochtonous (microbial polysaccharides) natural organic matter (NOM) on Pb speciation and bioaccumulation. The results demonstrated that polysaccharides, in particular alginic acid, had complexing properties and effects on Pb bioaccumulation by the green alga Chlorella kessleni that were similar to equivalent complexing capacity of humic substances. Pb uptake decreased in the presence of humic, alginic, and polygalacturonic acids with respect to noncomplexed Pb, but accumulated Pb was higher than predicted from measured Pb2+ concentrations or from previous results obtained in the presence of simple synthetic ligands. An improved fit between experimental observations and Pb speciation was obtained by taking into account the formation of a ternary complex at the algal surface. The contribution of the ternary complexes to Pb bioaccumulation was dependent on the relative binding constants of the Pb to the NOM and to the binding sites on the biological surface. In the presence of the humic acid, a decreased surface charge and increased membrane permeability were considered to be of secondary importance to explain the observation of increased Pb uptake with respect to that predicted on the basis of [Pb2+]. The environmental implications of the results are discussed with respect to the development of site-specific water quality criteria.