ThebehaviorofunpromotedandK-promotedFe/Al2O3 catalystsinboth,CO2 andCOhydrogenationreactionsat553–563K and 1.2MPa was compared. To attain different degrees of interaction between Fe and the support, three different procedures were followed to prepare the catalysts: impregnation, precipitation and physical mixing of the support with Fe oxide ob- tained from citrate decomposition. Fe-phase composition of pretreated (reduction-carburization) and after reactions catalysts was analyzed by Mössbauer spectroscopy. Correlation between Fe phase composition of pretreated catalysts and product selectivity was evident. A lower proportion of carbided Fe in fresh catalysts led to higher methane selectivity and higher alkanes/alkenes and internal/terminal alkenes ratios for both reactions, CO2 and CO hydrogenation. This relationship was observed independently of the reoxidation of carbide to magnetite, which took place during reactions for most catalysts. Lighter hydrocarbons were produced from CO2 hydrogenation compared to CO hydrogenation. Higher selectivities to C2–C4 alkenes were obtained from the first reaction through promotion with K. ©1999 Elsevier Science B.V. All rights reserved