χThe nanostructure of Fischer-Tropsch (FT) Fe carbides are investigated using aberration-corrected high-resolution transmission electron microscopy (TEM). The plasma-generated Fe carbides are analyzed just after synthesis, following reduction via a H2 treatment step and once used as FT catalyst and deactivated. The as-produced nanoparticles (NPs) are seen to be abundantly covered with graphitic and amorphous carbon. Using the extended information limit from the spherical aberration-corrected TEM, the NPs could be indexed as a mixture of NPs in the θ-Fe3C and χ–Fe5C2 phases. The reduction treatment exposed the NPs by removing most of the carbonaceous speSubscript textcies while retaining the χ–Fe5C2. Fe-carbides NPs submitted to conditions typical to FT synthesis develop a Fe3O4 shell which eventually consumes the NPs up to a point where 3-4 nm residual carbide is left at the center of the particle. Subscript textVarious mechanisms explaining the formation of such a microstructure are discussed.