This study investigated the effect of copper on chemical oxygen demand (COD) removal efficiency and on the properties (mainly settling and dewatering) and the composition of extracellular polymeric substances (EPS) when 20 mg/L Cu(II) was continuously dosed to a sequencing batch reactor (SBR) inoculated with activated sludge. The results showed that the continuous addition of 20 mg/L Cu(II) seriously inhibited the removal of sodium benzoate (provided as a model organic pollutant) by activated sludge in a SBR. After 40 days of acclimation, the removal efficiency presented a slight but unsteady recovery and the settling and dewatering properties improved, indicating that sludge bulking had been inhibited. Additionally, the proportion of loosely bound EPS in the total EPS increased with time and the relative composition of the total organics was polysaccharide > humic substances > protein > DNA. The effects of copper on the composition of EPS and the settling and dewatering properties of bulking activated sludge were also discussed for the first time in this paper.