A novel hollow fiber composite Nanofiltration (NF) membrane was fabricated by an improved preparation procedure. Using hollow fiber ultrafiltration (UF) membrane modules as the supporting modules, hollow fiber composite NF modules were fabricated by the one-step interfacial polymerization method. The effects of preparation conditions (such as concentration of the monomers, reaction time of monomers and ambient relative humidity, etc.) on the performance of the hollow fiber composite membranes were studied. When tested at 0.6 MPa, room temperature, the hollow fiber composite membrane had a rejection sequence of $MgSO_4$ > $Na_2SO_4$ > $MgCl_2$ > NaCl and a permeate flux sequence of NaCl > $Na_2SO_4$ > $MgSO_4$ > $MgCl_2$. The nagative charge character of the membrane surface was examined by streaming potential methods. The effect of the surface electrolyte properties on the membrane separation performance was investigated. The morphologies of the hollow fiber composite Nanofiltration membranes were studied by scanning electron microscopy (SEM) and atomic force microscopy (AFM).