Electrochemical and bioelectrochemical technologies are increasingly explored to address the coupled challenges of wastewater treatment and energy sustainability. Among them, electrocoagulation (EC) and microbial fuel cells (MFCs) represent fundamentally different yet potentially complementary approaches. EC removes pollutants through the in situ generation of coagulants from sacrificial metal electrodes, enabling rapid treatment of suspended solids, emulsified oils, dyes, and many dissolved metals. In contrast, MFCs use electroactive microorganisms to oxidize biodegradable organics at the anode and transfer electrons to a cathode, allowing simultaneous wastewater treatment and direct electricity recovery. Although both technologies have been widely studied independently, integrated comparisons addressing treatment performance, energy balance, material constraints, and scale-up remain limited, especially for MFC systems using ionic-liquid (IL)-based membranes. This critical comparative review evaluates EC and IL-membrane-based MFCs in terms of pollutant removal efficiency, operational flexibility, energy consumption versus recovery, by-product generation, long-term stability, and techno-economic feasibility. Particular attention is given to supported ionic liquid membranes and polymer/ionic-liquid composite separators as promising materials for reducing internal resistance, while also considering membrane fouling, oxygen crossover, and IL leaching. Overall, EC is highly effective for rapid depollution but remains energy- and material-intensive, whereas MFC deployment depends on stable, low-resistance, and environmentally safe IL-based membranes. Hybrid EC–MFC systems appear especially promising for robust, scalable, and resource-efficient wastewater treatment.