To understand how CO inhibits hydrogen transport across Pd membranes, a 25-μm-thick Pd foil membrane was monitored by infrared-reflection absorption spectroscopy (IRAS) during exposure to H2/CO gas mixtures while the rate of hydrogen permeation across the membrane was measured simultaneously in the 373–533 K temperature range. As the coverage of CO on the membrane surface increases with increasing CO concentration and decreasing temperature, the rate of hydrogen permeation across the membrane decreases. However, in addition to adsorbing on the membrane surface, CO reacts with H2 to form surface-adsorbed methylene (CH2) species and methane in the gas phase. The coverage of methylene increases with decreasing temperature and, therefore, the strong poisoning effect of CO at low temperatures may be due to both CO and methylene species blocking H2 dissociation sites on the membrane surface. The activity and selectivity of the Pd membrane for CO methanation is much higher than expected from previous studies and...