The slow kinetics of the electrochemical oxygen reduction reaction (ORR) is a crucial bottleneck in the development of microbial fuel cells (MFCs). This article firstly gives an overview of the particular constraints imposed on ORR by MFC operating conditions: neutral pH, slow oxygen mass transfer, sensitivity to reactive oxygen species, fouling and biofouling. A review of the literature is then proposed to assess how microbial catalysis could afford suitable solutions. Actually, microbial catalysis of ORR occurs spontaneously on the surface of metallic materials and is an effective motor of microbial corrosion. In this framework, several mechanisms have been proposed, which are reviewed in the second part of the article. The last part describes the efforts made in the domain of MFCs to determine the microbial ecology of electroactive biofilms and define efficient protocols for the formation of microbial oxygen-reducing cathodes. Although no clear mechanism has been established yet, several promising solutions have been recently proposed.