Hydrogen can be produced by bacterial fermentation of sugars, but substrate conversion to hydrogen is incomplete. Using a single-chamber microbial electrolysis cell (MEC), we show that additional hydrogen can be produced from the effluent of an ethanol-type dark-fermentation reactor. An overall hydrogen recovery of 83+/-4% was obtained using a buffered effluent (pH 6.7-7.0), with a hydrogen production rate of 1.41+/-0.08 m(3) H(2)/m(3) reactor/d, at an applied voltage of E(ap)=0.6 V. When the MEC was combined with the fermentation system, the overall hydrogen recovery was 96%, with a production rate of 2.11 m(3) H(2)/m(3)/d, corresponding to an electrical energy efficiency of 287%. High cathodic hydrogen recoveries (70+/-5% to 94+/-4%) were obtained at applied voltages of 0.5-0.8 V due to shorter cycle times, and repression of methanogen growth through exposure of the cathode to air after each cycle. Addition of a buffer to the fermentation effluent was critical to MEC performance as there was little hydrogen production using unbuffered effluent (0.0372 m(3) H(2)/m(3)/d at E(ap)=0.6 V, pH 4.5-4.6). These results demonstrate that hydrogen yields from fermentation can be substantially increased by using MECs.