Bioelectrochemical systems (BESs) are an emerging technology that uses solid‐state electrodes to stimulate microbial metabolism (either for substrate degradation or for products formation). Because of their versatility and unmatched level of control over the biological reactions, BESs hold a great potential for application in industrial and environmental bioprocesses. Among them, the bioelectrochemical production of renewable and carbon‐neutral energy carriers, such as hydrogen and methane, at the cathode of bioelectrochemical systems is recently attracting considerable attention. While exciting as a concept, the performance of the process seems to be still primarily limited by the low kinetics and efficiencies of the cathodic reactions. In this review, key opportunities for gaseous biofuels production with bioelectrochemical systems are addressed and compared with existing biotechnological approaches such as anaerobic digestion and dark fermentation. The major bottlenecks and challenges that still need to be faced to make this novel technology practical are presented and critically discussed. © 2012 Curtin University of Technology and John Wiley & Sons, Ltd.