Diamond thin films on Fe based materials (ferrous alloys) for the purpose of improving their surface properties such as wear and corrosion resistance have been investigated. There are main barriers restricting the quality and adhesion of diamond coatings on Fe based materials. Firstly, the incubation time of diamond nucleation is long due to the high solubility of carbon in Fe. Secondly, graphite soot forms before diamond nucleation due to the catalytic effect of Fe for formation of graphitic carbon. Thirdly, high internal stress remains at the interface which is induced by the large difference in the thermal expansion coefficients of diamond and most of the Fe based materials. Surface modification and interlayers are two important approaches to overcome these problems. In this work, the effect of Cr content in Fe-Cr alloys on diamond nucleation and growth is being studied in order to clarify the mechanisms of Cr in diamond deposition. Furthermore, in order to enhance the adhesion and quality of diamond coatings, Al based interlayers are being investigated on ferrous alloys. Fe-Cr alloys (with 20~80 wt.% Cr) were exposed to a CH4-H2 mixture in a microwave plasma enhanced chemical vapor deposition (MPCVD) reactor. Severe metal dusting and carburization were observed on the alloys with low Cr content and diamond did not nucleate on those alloys until a graphite intermediate layer had been formed, which takes a long incubation time. Increasing Cr concentration in the Fe-Cr alloys promotes the formation of a Cr carbide buffer layer, which inhibits metal dusting and the formation of graphite soot. Consequently, diamond nucleation and growth can be greatly enhanced, and continuous diamond films with enhanced adhesion have been deposited on the Fe-80Cr alloys. Al based interlayers including Al and Al/AlN interlayers were deposited on ferrous alloys (SS316 and Kovar: FeNiCo) to enhance diamond deposition. The deposition was carried out in a microwave plasma chemical vapor deposition (MPCVD) reactor using a CH4-H2 mixture. The obtained samples were characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), Raman spectroscopy, synchrotron-based X-ray absorption spectroscopy (XAS) and indentation testing. The results show that a single Al layer can effectively suppress the formation of graphite at the interface and the inward diffusion of carbon into Fe based substrates, and thereby enhances diamond nucleation and growth. The dual layers of Al/AlN can further enhance the adhesion of diamond coatings comparing with the single Al interlayer.