Academic Editor: Raf Dewil Copyright © 2019 Emna Feki et al. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. Disintegration of municipal waste activated sludge (WAS) using thermo-alkaline (TA) and electro-Fenton (EF) methods was investigated and compared in terms of the efficiency of sludge solubilisation and enhancement of anaerobic biodegradability. Performance of organic matter solubilisation (soluble COD, proteins, polysaccharides) of sludge pretreated with EF was proved to be better than that with TA pretreatment, which resulted in the enhancement of anaerobic biodegradability. Comparison of results indicated that percentages of PN and PS release obtained after EF pretreatment (68.95 and 65.22%) were higher than those obtained by TA method (45.25 and 35.22%) respectively. An improvement of biogas potential about 2 and 1.6 times was achieved respectively by EF and TA pretreatment in comparison to raw sludge. During semi-continuous fermentation study in continuous stirred tank reactor, EF pretreated sludge gave the best biogas yield (0.6 L biogas/g COD) at an OLR of 2.5 g COD/L. d in comparison to TA pretreated sludge (0.3 L biogas/g COD), where low biogas yield about 0.1 L biogas/g COD was registered by raw sludge in the same CSTR. Therefore, the integration of EF process to anaerobic digestion might be a promising process for sludge reduction and biogas recovery.