This study focuses on the experimental investigation to identify the effect of PAC at high concentrations on the fouling of membranes. A pilot-scale experimental apparatus was installed at a water treatment plant located downstream of Nakdong river basin, Korea. Effluent of rapid sand filter was used as influent of the system, which consists of PAC bio-reactor, submerged membrane module (hollow fiber with pore size 0.1 m) and air supply facility. PAC was dosed at 40 g/L initially and it was not replaced during the operation period. Suction type filtration was carried out at intervals of 12 min. suction and 3 min. idling. At the initial flux 0.36 m/d, the system could be operated stably for around 90 days at target trans-membrane pressure (TMP) of 40 kPa. Among total resistance of membrane filtration, cake and gel layer resistance, Rc+Rg, was the dominant fraction (more than 90% of the total) to increase the filtration pressure, which means that the filtration resistance could be controlled by the PAC cake layer and then irreversible membrane fouling could be prevented. Three minutes air backwashing every 3 days could extend the operation period to 127 days. Organics were analyzed in terms of molecular weight structure. The influent of the system consists of 15.0% and 74.4% of hydrophobic and hydrophilic natural organic matter (NOM), respectively. Hydrophobic and hydrophilic (electrostatic) interaction was the main factor on fouling of the membrane in the reactor. Hydrophobic fraction decreased slightly in the effluent, which means hydrophobic NOM removal in the reactor by adsorption. Organics accumulated in the membrane were extracted for analysis after a certain period of operation. The fraction of hydrophobic and hydrophilic organics was 41.4% and 38.9%, respectively. On the basis of the experimental results, the hydrophobic organics were the major materials causing the fouling of the membrane, which should be changed to other types of material.