Anaerobic digestion of waste activated sludge was conducted to gain insight into the mechanisms underlying change in sludge dewaterability during its anaerobic digestion. Unexpectedly, the results indicated that sludge dewatering properties measured by capillary suction time only deteriorated after 10 days of anaerobic digestion, after which dewaterability recovered and remained stable. The loosely bound extracellular polymeric substance (LB-EPS) content increased three-fold after 20 days of anaerobic digestion, and did not change significantly during the remaining 30 days. The tightly bound EPS (TB-EPS) content reduced slightly after 20 days of anaerobic digestion, and stabilized during the last 30 days. Polysaccharides (PS) and proteins (PN) content in LB-EPS increased after 10 days of anaerobic digestion. However, PS and PN contents in TB-EPS decreased slightly. The relationship analysis showed that only LB-EPS correlated with dewaterability of the sludge during anaerobic digestion.