The aerobic granular sludge technology has a great potential in treatment of municipal wastewater and industrial wastewater containing toxic non-degradable pollutants. However, the formation and structural stability of aerobic granular sludge is susceptible to toxic shock. In the study, the effect of 4-chloroaniline (4-ClA) as a common toxic pollutant on the granular structure and performance was investigated, and the mechanism was revealed to provide more information on 4-ClA degradation with aerobic granular sludge process. The results showed that a 4-ClA shock at influent 200 mg L-1 could cause the disintegration of aerobic granular sludge and decrease of the pollutant removal performance. The analysis of extracellular polymeric substances (EPS) within the mature and disintegrated granular sludge showed that the decrease of protein content in EPS, especially the components like Amide I 3-turn helix and beta-sheet structures and aspartate, was not good for the stability of aerobic granular sludge. The microbial community results demonstrated that the disappearance of dominant bacteria like Kineosphaera limosa or appearance like Acinetobacter, might contribute to the reduction of EPS and disintegration of aerobic granular sludge. (C) 2013 Elsevier Ltd. All rights reserved.