Mossbauer spectroscopy studies of precipitated Fischer-Tropsch (FT) iron catalysts, viz. 100 Fe/5 Cu/4.2 K/x SiO2, wherex=0,8, 16, 24, 25, 40, or 100, have shown that reduction of the oxide precursor in CO gives rise to χ-carbide Fe5C2 whose amount decreases with an increase of SiO2 content. The χ-carbide is converted into magnetite Fe3O4 while catalyzing the FT synthesis reaction. A correlation between FT activity and the content of χ-carbide in the catalysts was found, which indicated that χ-carbide is active for FT synthesis reaction.