A polyethersulfone ultrafiltration membrane was functionalized by a cationic polyelectrolyte, the poly(allylamine) hydrochloride (PAH). The influence of the time of adsorption of PAH on the membrane charge properties was studied. Several characterization techniques were used to investigate the membrane modification. Tangential and transmembrane streaming potential measurements were conducted to characterize the outer and inner surfaces of the membrane, respectively. Both techniques indicated that the surface modification of the membrane was efficient. The charge of the outer surface was reversed (from negative values for the unmodified membrane to positive values for the modified membrane) and the charge of the inner surface was neutralized after adsorption of the cationic polyelectrolyte onto the pore walls. The modification of both the outer surface of the membrane and the pore walls was also put in evidence with membrane potential measurements. It was found that the charge of the PAH-modified membrane is affected by the time of immersion in PAH solution. Experimental data seem to show a fast modification of the membrane for the first 15 min; nevertheless, the modification was more pronounced after 24 h of PAH adsorption. Diffusion experiments carried out with unmodified and modified membranes for four salts (KCl, NaCl, MgCl, and CaCl(2)) showed a decrease in the salt permeability after functionalization of the membrane. The permeability decrease was greater for 2:1 salts than for 1:1 salts. This decrease was explained by electrostatic interactions.