An excellent positively charged nanofiltration (NF) membrane is of great significance for water softening. In this work, a novel positively charged composite PEI/TMA NF membrane was prepared by gradient cross-linking polyethyleneimine (PEI) with trimesic acid (TMA) on polyethersulfone ultrafiltration (PESU) membrane. The effects of concentration of PEI and TMA, the cross-linking reaction temperature and reaction time on membrane structure and performance were investigated in detail. The effects of PEI and TMA, reaction temperature and time on the membrane structure, composition and performance were investigated. The optimized preparation conditions of PEI/TMA NF membrane were fixed at 0.6% (m/v) PEI, 0.1% (m/v) TMA, 0.15% (m/v) SDS at 90 degrees C for 10 min. The as-prepared membrane exhibited a pure water flux of 19.1 L m(-2) h(-1) bar(-1) and a rejection of MgCl2 93.0%, NaCl 38.2%, MgSO4 20.4%, and Na2SO4 8.8%. The functional layer is ultra-thin. Its high selectivity mainly results from Donnan effect. The long-term testing of our PEI/TMA NF membrane show a high stability. Compared with other positively charged membranes, the PEI/TMA NF membrane had unique advantages in the production process and a comprehensive performance.