Polyethyleneimine (PEI) of various molecular weights and trimesoyl chloride (TMC) were utilized to prepare composite nanofiltration (NF) membranes via interfacial polymerization. The changes in the surface structure and chemical composition of the prepared membranes were evaluated using SEM, ATR-FTIR, XPS and surface potential measurements. The pure-water flux and rejection rates of the inorganic salts (MgCl2, MgSO4, Na2SO4 and NaCl) through the resultant NF membranes were also investigated. The results showed that the performance of the composite NF membranes was significantly affected by the molecular weight of the PEI. Notably, the permeate flux and rejection rate of the NF membranes increased with the PEI molecular weight. In addition, when the NF membranes were used to treat actual wastewater from the electroplating industry, the NF membranes presented high-efficiency separation properties for heavy metal ions. The rejection rates of the NF membranes at 0.4 MPa for chromium, nickel, zinc and copper ions reached 92.6, 89.6, 89.2 and 86.3%, respectively.