In less than a decade, bioelectrochemical systems/microbial fuel cell integrated constructed wetlands (electroactive wetlands) have gained a considerable amount of attention due to enhanced wastewater treatment and electricity generation. The enhancement in treatment has majorly emanated from the electron transfer or flow, particularly in anaerobic regions. However, the chemistry associated with electron transfer is complex to understand in electroactive wetlands. The electroactive wetlands accommodate diverse microbial community in which each microbe set their own potential to further participate in electron transfer. The conductive materials/electrodes in electroactive wetlands also contain some potential, due to which, several conflicts occur between microbes and electrode, and results in inadequate electron transfer or involvement of some other reaction mechanisms. Still, there is a considerable research gap in understanding of electron transfer between electrode-anode and cathode in electroactive wetlands. Additionally, the interaction of microbes with the electrodes and understanding of mass transfer is also essential to further understand the electron recovery. This review mainly deals with the electron transfer mechanism and its role in pollutant removal and electricity generation in electroactive wetlands.