Microbial fuel cell (MFC) is an emerging technology for sustainable energy generation and waste treatment. This paper reviews the potential of a gaseous substrate when it is combined with a mediator in an MFC to generate electricity and to treat toxic gaseous pollutants. Most MFCs for waste water treatment often cannot use mediator to enhance the electron transfer from the microbe to the anode because of the difficulty in recovering the expensive and potentially toxic compound. Combining gas feeds with mediators is possible since the soluble mediator would remain in the anode chamber as the gas passes through the reactor. In addition, this type of MFC is possible to be integrated into an anaerobic biofiltration system (BF-MFC), where the biofilter removes the gaseous contaminant and produces the reduced mediator and the MFC produces the electricity and recycles the reoxidised mediator. This paper also talks about the past research on gaseous feed MFCs, and reviews the mechanism and strategies of electron transfer in MFC using redox mediator. The advantages, process parameters and challenges of BF-MFC are discussed. This knowledge is very much required in the design and scale up of BF-MFC. This paper will be useful for those who work in the area of gaseous pollutant treatment and electricity generation.