Fractional separation of industrially important heavy metals (cadmium, nickel, zinc) from binary and ternary metal mixtures by continuous mode polymer enhanced ultrafiltration was studied. Polyethyleneimine (PEI) was used as a complexation polymer. Effects of pH and ionic strength on process efficiency were investigated. To gain insight about the characteristics of binding between highly branched PEI and metal ions and effect of salt concentration on this binding were investigated by performing dynamic and static light scattering measurements. It was observed that with optimum pH and salt concentration, fractional separation of metals can be achieved.