The development of clean borderless fuels is of vital importance to human and environmental health and global prosperity. Currently, fuels make up approximately 67% of the global energy market (total market = 15 TW year−1) (Hoffert et al. 1998). In contrast, global electricity demand accounts for only 33% (Hoffert et al. 1998). Yet, despite the importance of fuels, almost all CO2 free energy production systems under development are designed to drive electricity generation (e.g. clean-coal technology, nuclear, photovoltaic, wind, geothermal, wave and hydroelectric). In contrast, and indeed almost uniquely, biofuels also target the much larger fuel market and so in the future will play an increasingly important role in maintaining energy security (Lal 2005). Currently, the main biofuels that are at varying stages of development include bio-ethanol, liquid carbohydrates [e.g. biodiesel or biomass to liquid (BTL) products], biomethane and bio-H2. This review is focused on placing bio-H2 production processes into the context of the current biofuels market and summarizing advances made both at the level of bioengineering and bioreactor design.