The effects of pH, hydrogen partial pressure (PH2), and influent glucose concentration on the metabolic distribution in chemostat were investigated in this work in extreme-thermophilic mixed culture fermentation (MCF) process. The results showed that acetate, ethanol, and hydrogen were the main metabolites. A shift of ethanol to acetate and hydrogen was observed as pH increasing from 4.0 to 7.0 or PH2 decreasing from 0.64 to 0.05 atm. The maximum hydrogen yield was 3.16 ± 0.16 mol/mol glucose at PH2 0.05 atm. Lactate was only accumulated at low pH or high influent glucose concentration, while others such as butyrate and formate were rather low. Thermodynamic analysis illustrated that a mixture of acetate, ethanol, and/or lactate was essential for hydrogen production in extreme-thermophilic MCF. The hydrogen-producing rate was also calculated, and the maximum value was 2.2 ± 0.1 L/(L-reactor/day) at PH2 0.05 atm. Except hydrogen, other metabolites, such as liquid fatty acids and biofuels, could also be the producing targets in extreme-thermophilic MCF.