The single-chamber membrane-less MEC exerted much better hydrogen production performance while given higher applied voltages than it did at lower. High applied voltages that could shorten the reaction time and the exposure of anode to air for at least 30 min between cycles can significantly suppress methanogen and increase hydrogen production. At an applied voltage of 1.0 V, a hydrogen production rate of 1.02 m(3)/m(3)/day with a current density of 5.7 A/m(2) was achieved. Cathodic hydrogen recovery and coulombic efficiency were 63.4% and 69.3% respectively. The hydrogen concentration of mixture gas produced of 98.4% was obtained at 1.0 V, which was the best result of reports. The reasons that such a high hydrogen concentration can be achieved were probably the high electrochemical activity and hydrogen production capability of the active microorganisms. Increase in substrate concentrations could not improve MEC's performance, but increased the reaction times. Further, reactor configuration and operation factors optimisation should be considered to increase current density, hydrogen production rate and hydrogen recovery.