Several polyethersulfone (PES) ultrafiltration membranes have been made with small quantities of polyvinyl-pyrrolidone (PVP) of different molecular weights to increase the permeability without a significant reduction in selectivity. The corresponding fouling mechanism and subsequent structural modifications have been analyzed when in contact with bovine serum albumin (BSA) and DL-histidine (DLH). It has been shown that according to the relative sizes of solute and pores of the membranes: BSA fouls the three membranes externally whereas DLH fouls them internally. Moreover, BSA fouls the non-PVP membranes faster than DLH fouls them slower, according to the action of hydrophobic and electrostatic forces acting at the, working pH (4.9). The changes in structure, remaining after water rinsing, is quite similar for the three membranes and both the solutes, as obtained by a retention test of adequate polyethylene glycols (PEGs). (C) 2002 Elsevier Science B.V. All rights reserved.