Formation of methane in the anodic chamber of a microbial fuel cell (MFC) indicates an energy inefficiency in electricity generation as the energy required for electrogenesis gets redirected to methanogenesis. The hypothesis of this research is that inhibition of methanogenesis in the mixed anaerobic anodic inoculum is associated with an enhanced activity of the electrogenic bacterial consortia. Hence, the primary objective of this investigation is to evaluate the ability of chloroform to inhibit the methanogenesis at different dosing to enhance the activity of electrogenic consortia in MFC. A higher methane inhibition and hence an enhanced performance of MFC was achieved when mixed anaerobic sludge, collected from septic tank, was used as inoculum after pre-treatment with 0.25% (v/v) chloroform dosing (MFC-0.25CF). The MFC-0.25CF attained a maximum power density of 8.51 W/m3, which was more than twice as that of MFC inoculated with untreated sludge. Also, a clear correlation between the chloroform dosing, methane inhibition, wastewater treatment, and power generation was established, which demonstrated the effectiveness of the technique in enhancing power generation in MFC along with adequate biodegradation of organic matter present in wastewater at an optimum chloroform dosing of 0.25% (v/v) to inhibit methanogenesis.