Alginate-like exopolymers (ALE) are present in the extracellular polymeric substances (EPS) of biological sludge such as aerobic granular sludge (AGS). The recovery of ALE from excess sludge produced by wastewater treatment plants (WWTP) is a relevant approach for the recovery of valuable products of industrial interest. However, little is known about dynamics of ALE content in sludge and associated factors. Thus, this study aimed at assessing the dynamics of EPS and ALE in terms of content, some chemical properties and influencing environmental factors along granulation in a sequencing batch reactor treating municipal wastewater. Results indicated that the EPS content was not correlated with the development of AGS, while the ALE content was higher, more stable and steadily increased after granulation achievement. Overall, 236 ± 27 mg VS_ALE/g VS_sludge was recovered from AGS and 187 ± 94 mg VS_ALE/g VS_sludge from flocs. However, the lower ALE content in flocs may be compensated by the higher sludge production rate in activated sludge systems. Principal component analysis (PCA) revealed that ALE content positively correlates with the nutrient and organic substrate conversion, and with the fraction of large AGS. Microbial analyses indicated that a stable microbial community composition was associated with a higher and more stable ALE content. ALE recovered from both flocs and AGS was endowed with hydrogel property, and no clear difference in their elemental composition and functional groups was observed. Therefore, our study provides insights about quantitative and qualitative aspects of ALE which are helpful for the improvement of waste biological sludge valorization.