Diamond growth on Fe-Cr-Al-Si steel and Si substrates was comparatively investigated in microwave plasma enhanced chemical vapor deposition (MPCVD) reactor with different deposition parameters. Adherent nanocrystalline diamond films were directly deposited on this steel substrate under a typical deposition condition, whereas microcrystalline diamond films were produced on Si wafer. With increasing CH4 concentration, reaction pressure, or the total gas flow rate, the quality of nanocrystalline diamond films formed on Fe-Cr-Al-Si substrates is gradually deteriorated in terms of density and adhesion. This impaired diamond quality on steels is primarily associated with a combined effect by the substrate composition and the specific process conditions that favor excessive nucleation of diamond.