The electro-Fenton (EF) disintegration using iron electrodes was performed for the pretreatment of waste acti-vated sludge (WAS). The effect of this electro-chemical pretreatment on anaerobic digestion (AD) performance and microbial population structure was studied. An improvement of biodegradability and bioaccessibility of organic matter was demonstrated. AD of pretreated WAS in an up-flow anaerobic sludge blanket reactor (UASB) resulted to an increase of biogas production by 60 % compared to control reactor without disintegration. PCR-DGGE and real-time qPCR analyses showed that the high abundance of bacteria and the coexistence of Cop-rothermobacter in the UASB digestate fed with disintegrated sample established a stable bacterial association which is in line with the AD performance. Besides, the increased number of methanogens along the process allowed the improvement of methane production in comparison to control reactor.