Four nanofiltration membranes, two negatively and two positively charged, were fabricated by interfacial polymerization. Three different amines, ethylenediamine (EDA), diethylenetriamine (DETA), and hyperbranched polyethyleneimine (PEI) were selected to react with two acyl chlorides, trimesoyl chloride (TMC) and terephthaloyl chloride (TPC). The two membranes containing hyperbranched PEI, PEI/TPC and PEI/TMC, are positively charged at the operational pH. But the other two membranes, EDA/TMC and DETA/TMC, are negatively charged. It is found that the two PEI membranes own special rejection characters during nanofiltration. The PEI/TPC membrane has a similar pore size to the EDA/TMC membrane but owns simultaneously the higher salt rejection and permeation flux. The PEI/TMC has a pore size as large as 1.5 nm and still has a higher NaCl rejection than the EDA/TMC membrane of which the pore size as small as 0.43 nm. We consider that the special rejection characters are derived from the special structure of PEI. The hyperbranched structure allows some of the charged amine groups drifting inside the pores and interacting with the ions in the pathway. The drifting amines increase salt rejection but have little effect on water permeation. It implies that a high flux and high rejection membrane for desalting can be obtained by attaching freely rotating charged groups. (C) 2008 Elsevier B.V. All rights reserved.