Anaerobic digestion (AD) appears to be a popular unit operation in wastewater treatment plant to treat waste activated sludge (WAS) and the produced methane gas can be harvested as renewable energy. However, WAS could inhibit hydrolysis stage during AD and hence pre-treatment is required to overcome the issue. This paper aimed to study the effect of electrochemical pre-treatment (EP) towards efficiency of AD using titanium coated with ruthenium oxide (Ti/RuO2) electrodes. The investigation has been carried out using in-house laboratory batch-scale mesophilic anaerobic digester, mixed under manipulation of important operating parameters. Optimization was performed on EP using response surface methodology and central composite design to maximize sludge disintegration and dewaterability. By operating at optimal conditions (pH 11.65, total solids 22,000 mg/L, electrolysis time 35 min, current density 6 mA/cm2, and 1000 mg/L of sodium chloride), the pre-treated WAS in terms of mixed liquor volatile suspended solids (MLVSS) removal, soluble chemical oxygen demand (sCOD), capillary suction time (CST) reduction, and extracellular polymeric substance (EPS) were 38%, 4800 mg/L (increased from 935 mg/L), 33%, and 218 mg/L, respectively. Following AD, the volatile solids (VS) removal and chemical oxygen demand (COD) removal by EP were enhanced from 40.7% and 54.7% to 47.2% and 61.5%, respectively, at steady-state. The biogas produced from control and electrochemical pre-treated WAS were in the ranges of 0.12 to 0.17 and 0.2 to 0.24 m3/kg VSfed, respectively, and the volume of biogas produced was 44–67% over the control. Based on the results obtained, suitability of EP for WAS prior to AD was confirmed.