Steam reforming of ethanol in the membrane reactor using the Pd77Ag23 membrane was evaluated in Ni/CeO₂ and Co/CeO₂ at atmospheric pressure. At 673 K, the H₂ yield in the Pd77Ag23 membrane reactor over Co/CeO₂ was found to be higher than that over Ni/CeO₂, although the H₂ yield over Ni/CeO₂ exceeded that over Co/CeO₂ at 773 K. This difference was owing to their reaction mechanism. At 773 K, the effect of H₂ removal could be understood as the equilibrium shift. In contrast, the H₂ removal kinetically inhibited the reverse methane steam reforming at low temperature. Thus, the low methane-forming reaction rate of Co/CeO₂ was favorable at 673 K. The addition of a trace amount of Ru increased the H₂ yield effectively in the membrane reactor, indicating that a reverse H₂ spill over mechanism of Ru would enhance the kinetical effect of H₂ separation. Finally, the effect of membrane performance on the reactor performance by using amorphous alloy membranes with different compositions was evaluated. The H₂ yield was set in the order of H₂ permeation flux regardless of the membrane composition.