The aerobic granular sludge was cultivated in a pilot-scale sequencing batch reactor (SBR), and some of the granules were stored at 8 ℃ for 150 d. Extracellular polymeric substances (EPS) of sludge samples were extracted and analyzed during the granulation and storage process. The results show that the contents of protein and EPS increase along with the granulation process, while polysaccharides remain almost unchanged. The content of protein in EPS is almost two-fold larger than that of polysaccharides in granular sludge cultivated with municipal wastewater. Moreover, some of the granules disintegrate during storage, corresponding to the decrease of protein contents in EPS. Three peaks are identified in three-dimensional excitation emission matrix (EEM) fluorescence spectra of the EPS in the aerobic granules. Two peaks (A and B) are attributed to the protein-like fluorophores, and the third (peak C) is related to visible fulvic-like substances. Peak A gradually disappears during storage, while a new peak related to ultraviolet fulvic acid (peak D) is formed. The formation and the stability of aerobic granules are closely dependent on the quantity and composition of EPS proteins. Peak C has no obvious changes during granulation, while the fulvic-like substances present an increase in fluorescence intensities during storage, accompanied with an increase in structural complexity. The fulvic-like substances are also associated with the disintegration of the aerobic granules.