In MBR, extracellular polymeric substance (EPS) is known as an important factor of fouling; soluble EPS (sEPS) affects internal contamination of membrane, and bound EPS (bEPS) affects the formation of the cake layer. The production of EPS changes according to the composition of influent, which affects fouling characteristics. Therefore, in this study, the effects of the F/M ratio on the sEPS concentration, bEPS content, and fouling were evaluated. The effects of F/M ratio on the amount and composition of EPS were confirmed by setting conditions that were very low or higher than the general F/M ratio of MBR, and the fouling occurrence characteristics were evaluated by filtration resistance distribution. As a result, it was found that the sEPS increased significantly with the increase of the F/M ratio. When the substrate was depleted, bEPS content decreased because bEPS was hydrolyzed into BAP and seemed to be used as a substrate. In contrast, when the substrate is sufficient, UAP (utilization-associated products) was rapidly generated in proportion with the consumption of the substrate. UAP has a relatively higher Protein/Carbohydrate ratio (P/C ratio) than BAP, and this means, it has a higher adhesive force to the membrane surface. As a result, UAP seems like causing fouling rather than BAP (biomass-associated products). Therefore, Rf (Resistance of internal contamination) increased rapidly with the increase of UAP, and Rc (Resistance of cake layer) increased with the accumulation of bEPS in proportion, and as a result, the fouling interval was shortened. According to this study, a high F/M ratio leads to an increment in UAP generation and accumulation of bEPS, and by these UAP and bEPS, membrane fouling is promoted.