The effect of sodium bromide (NaBr) on performance and characteristics of ultrafiltration (UF) membranes was studied. Asymmetric UF membranes were prepared by phase inversion technique from a multicomponent dope polymer solution consisting of the polymer; polyethersulfone (PES), solvent; N, N‐dimethylformamide (DMF) and NaBr as micromolecular additive. The dissolution of PES‐DMF‐NaBr was carried out using microwave irradiation technique to induce rapid dissolution through minimal heating time. Various concentrations of NaBr were mixed with PES in the range of 1–5 wt % and its influence on membrane characteristics such as surface hydrophilicity was measured by contact angle and the performance in terms of water flux and rejection rates were evaluated using micromolecular test substances. The morphology and streaming potential of PES UF membranes were analyzed using scanning electron microscopy (SEM) and ζ‐potential measurement, respectively. Overall, the results suggest that the membrane consisting of 1 wt % NaBr exhibits the best performance in terms of rejection and flux rates with molecular weight cutoff (MWCO) of 45 kDa and mean pore size of 6 nm. The membrane with the 1 wt % addition of NaBr demonstrates most negative charge which indicates less fouling characteristics and displays approximately three times higher permeation. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013