Anaerobic digestion (AD) is a promising technology capable of converting waste matter into bio-energy. Recent studies have reported that microbial electrolysis cell assisted anaerobic digestion (MEC-AD) is an effective system for methane production from organic waste, via enhanced electron transfer. However, little is known about the effects of applied voltage on the AD of proteins. Herein, the mechanism of MEC-AD on protein digestion was investigated using varying concentrations of bovine serum albumin (BSA) as the protein substrate (500 mg/L, 4 g/L, and 20 g/L BSA). Experimental results showed that the applied voltage can not only enhance the methane production rate from 23.8% to 45.6% at low and medium organic loading (BSA concentration of 500 mg/L and 4 g/L), but also improve the methanogenesis efficiency increased by 225.4% at high BSA concentration (20 g/L) with the applied voltage of 0.6 V compared to that with open circuit. Mechanism explorations revealed that the applied voltage significantly enhanced the acidogenesis and methanogenesis processes in the AD of proteins. Microbial community characterization showed that with the applied voltage, the abundance of fermentative bacteria increased by 46.7 % at the anode, while, the abundance of Methanobacterium at the cathode increased from 10.4 to 84.3%, indicating the methanogenesis pathway transformed from acetoclastic to hydrogenotrophic. External circuit electron transfer calculations demonstrated that only 10% of the produced methane could be attributed to direct interspecies electron transfer (DIET). From a thermodynamic perspective, the applied external voltage led to a reduction in the cathodic potential to -0.9 V, which is beneficial for enhanced methane production via mediated interspecies electron transfer (MIET) by enrichment of hydrogenotrophic methanogens. The findings reported here reveal the previously unrecognized contribution of proteins to MEC-AD, while also furthering our understanding of the role of applied voltage in the MEC-AD process.