A PES-based composite nanofiltration membrane was prepared by spreading a thin layer of sodium tripolyphosphate (STPP)-modified chitosan (CS) on a PES membrane. Two approaches of modification were employed: coating, and injecting the chitosan solution into PES membrane by applying pressure. Physicochemical properties of the prepared membranes were characterized by FTIR-ATR, zeta potential, contact angle, AFM and FE-SEM methods. AFM images showed a denser and more compact surface for STPP-modified membranes compared to the unmodified one. The membranes prepared by the second approach illustrated favorable properties: the increase of both flux and rejection. Engaging of -NH2 groups in CS with polyanionic phosphate groups of STPP resulted in less availability of functional groups. Furthermore, denser and relatively higher positively charged surface could be the main reasons for higher rejection of membrane composed of 0.05wt% STTP towards copper ions in comparison with the other membranes. Furthermore, the presence of SO4 2- ions in the CuSO4 solution slightly changed the positive charge of the membrane surface, resulting in tangible variations in rejection. According to the Donnan exclusion theory, relative increase of the negative charge of the surface in the presence of the highest concentration of STTP caused less NaCl and CuSO4 rejection compared to the other STPP modified membranes.