Continuous and batch processes of polymer enhanced ultrafiltration for the estimation of binding constants of divalent cadmium, nickel, and zinc ions have been elaborated. Polyethyleneimine was used as a complexation agent. Effect of pH and ionic strength on the binding ability of target metal ions to polyethyleneimine were estimated by continuous mode PEUF system. A mathematical model was developed to estimate apparent complexation constants of metal ions with PEI. The development of this model, which is in good agreement with experimental data, enables to compare the data obtained in both continuous and batch system and correlate the effect of pH and ionic strength with apparent binding constants.