We examined the promotion effect of Fe addition and the role of Fe on Co/alpha-Al2O3 catalyst for ethanol steam reforming using XAFS and IR. Activity tests of Fe/Co/alpha-Al2O3 with various Fe loadings show the addition of 0.22 wt% iron as an appropriate amount for the promotion of ethanol steam reforming. The investigation of apparent activation energies revealed that both ethanol steam reforming and acetaldehyde steam reforming were promoted by 0.22 wt%Fe addition. XAFS analyses revealed that Co and Fe on 0.22 wt%Fe/Co/alpha-Al2O3 produced Co-Fe alloy with an fcc-structure. Results of in situ IR measurements showed that acetate species were stabilized on the catalyst by loading 0.22 wt%Fe, and that the catalytic activity and selectivity to hydrogen were improved by Fe addition. (C) 2013 Elsevier B.V. All rights reserved.