Thin iron carbide films were prepared by introducing iron penta carbonyl (FeCO5) and hydrogen (H2) into a glow discharge. The films are of potential interest in corrosion and wear resistant applications. X-ray diffraction data of films (≈ 7000 Å thick) deposited on glass at 300°C evidenced only Fe7C3. Thinner films were required for examination by analytical and high resolution transmission electron Microscopy. Therefore, two sets of films (“thin” < 200 Å and “thick” ≈ 800 Å) were plasma-deposited on carbon or holey carbon films supported on copper grids. The thin TEM specimens exhibited a fine texture and gave rise to ring diffraction patterns, whereas the thick TEM specimens evidenced two types of structure: (i) half-Micron sized grains separated from one another by 1–2 Microns on the support, although sometimes interconnected by single crystal platelets and (ii) 300 Å grapelike clumps of 100–200 Å crystals, each individually surrounded by a 50 Å non-crystalline coating. The latter structure may result from a post-formation oxidation process which expels carbon from the iron phase into grain boundaries.