Negatively charged CMPES and positively charged QAPES membranes were fabricated. Charge modification reduced the adhesion forces between PES UF membranes and BSA. QAPES-BSA / was weaker than that of CMPES-BSA at pH 3 and on the contrary at pH 9. Flux decline rate was positively correlated with the adhesion forces of membrane-BSA. Variation of adhesion was consistent with that of potential absolute values. Negatively charged carboxymethylated polyethersulfone (CMPES) and positively charged quaternized polyethersulfone (QAPES) ultrafiltration (UF) membranes were prepared by bulk chemical modification and non-solvent induced phase separation method. The effects of PES membrane interfacial electrokinetic property on the bovine serum albumin (BSA) membrane fouling behavior were studied with the aid of the membrane-modified colloidal atomic force microscopy (AFM) probe. Electrokinetic test results indicated that the streaming potential (D ) of QAPES membrane was not consistent with its expected value, however, within the pH range of 3–10, the potentials of two charged-modified PES membranes were more stable than the unmodified membrane. When pH value was 3, 4.7 or 9, the interaction behavior between charged PES membrane and BSA showed that there was significant linear correlation between the jump distance of membrane-BSA adhesion force ( ) and the potential absolute value. Charged modification significantly reduced the adhesion of PES membrane-BSA, and the adhesion data was good linear correlated with the flux decline rate in BSA filtration process, especially reflected in the CMPES membrane. The above experimental facts proved that the charged membrane interfacial electric double layer structure and its electrokinetic property had strong ties with the protein membrane fouling behavior.