The size distributions of zinc and copper species in the effluent of a wastewater treatment plant were determined by a combination of ultrafiltration and chelating disk cartridge fractionation. The results showed that 75–87% of total Zn and 84–86% of total Cu were strongly complexed or particle-bound in the final effluents. It was also found that the major part of Cu was bound to ligands in the <500 Da fraction while the trend for Zn was not so clear and exhibited significant seasonal variability. Labile Cu and Zn were detected not only in the smallest fraction (<500 Da) but also in the larger fractions. It meant that the labile species in the effluent were not equivalent to free metal ions. Conditional stability constants and ligand concentrations were also determined from the measured metal concentrations by square wave anodic stripping voltammetry. Existence of two types of ligand for each metal was inferred from the experimental data. Conditional stability constant obtained for the stronger type Ligand of Zn was higher than that of Cu, although the estimated Ligand concentrations were almost similar.