Extra-cellular polymeric substances (EPS), known to contribute to fouling in membrane bio-reactors (MBRs), are generally divided into bound and free EPS. The free EPS are able to form a gel layer on the membrane active surface. The mechanisms involved in formation of such layer and its effects on performance of the MBR membranes were studied. The free EPS, extracted by centrifugation and microfiltration, contained a significant amount of humic-like substances. Under static contact to the membrane, adsorption of humic-like substances to the membrane occurred and could be explained by conventional adsorption kinetics. Due to static adsorption, surface roughness of the membrane declined significantly, indicating that adsorbed matters to the membrane filled the cavities of the membrane surface. Filtration of the free EPS caused 50% water flux decline. The fouling resistance linearly increased with the amount of the humic-like substances retained during filtration as predicted by gel growth theory. A low pressure backwash could re-establish the water flux only up to 70%.