This study investigates the removal of Pb(II) using polymer matrix membranes, cellulose acetate/vinyl triethoxysilane modified graphene oxide and gum Arabic (GuA) membranes. These complexation-NF membranes were successfully synthesized via dissolution casting method for better transport phenomenon. The varied concentrations of GuA were induced in the polymer matrix membrane. The prepared membranes M-GuA2–M-GuA10 were characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, transmission electron microscopy, atomic force microscope and bio-fouling studies. Thermal stability of the membranes was determined by thermogravimetric analysis under nitrogen atmosphere. Dead end nanofiltration was carried out to study the perm- selectivity of all the membranes under varied pressure and concentration of Pb(NO3)2. The complexation-NF membrane performances were significantly improved after the addition of GuA in the polymer matrix membrane system. M-GuA8 membrane showed optimum result of permeation flux 8.6 l m−2 h−1. Rejection of Pb(II) ions was observed to be around 97.6% at pH 9 for all the membranes due to electrostatic interaction between CA and Gum Arabic. Moreover, with the passage of time, the rate of adsorption was also increased up to 15.7 mg g−1 until steady state was attained. Gum Arabic modified CA membranes can open up new possibilities in enhancing the permeability, hydrophilicity and anti-fouling properties.