Data on the concentrations and movements of Zn, Pb and Cd in Dnieper reservoirs and the Dnieper‐Bug estuary are considered. There is a clear trend of increasing concentrations, often two‐ to fourfold, of these materials from the 1960s to the end of the 1980s. Large increases may be explained as the result of increased human impact on the water‐bodies and also because of reduced water discharge in the Dnieper River (discharge has been reduced by nearly 10 km3 in recent years). At present, the average concentrations of Zn, Pb and Cd in Dnieper water‐bodies are 35.0–50.0, 15.0–18.0 and 0.5–1.8 μg L–1, respectively. Anodic stripping voltammetry, membrane filtration, ion‐exchange and gel permeation chromatography on neutral sephadexes were methods used for analysis. The influence of adsorption and complexation processes on the mobility of Zn, Pb and Cd, and the ratio of their forms were compared. Ratios of free metal ions to ions bound in complexes with natural organic ligands were studied. The binding of metals in complexes with dissolved organic matter (DOM), or their adsorption onto suspended particles, were major processes reducing the concentration of free ions in their most toxic form. The percentage of Zn, Pb, and Cd free ions in the total balance of dissolved forms was no more than 3.6–4.8, 0.2–0.6 and 7.2–9.5%, respectively. The molecular‐weight distribution of organic metal complexes and their chemical nature, as well as the potential for complexing of DOM were investigated. Most Zn, Pb and Cd was found as complex compounds with DOM of different chemical natures and molecular weights. Humic substances, particularly fulvic acids, played a major role in the migration of the metals. These ligands bind from 40 to 80% of metals in the composition of organic complexes. Metal complex compounds of relatively low molecular weight (< 5000 Da) predominated in organic complexes of Zn (38–50%), Pb (38–52%) and Cd (22–47%). The role of inorganic ligands in complexation in surface waters was less important.