Chemical vapor deposition (CVD) has been the main method for synthesizing diamond thin films on hetero substrate materials since 1980s. It has been well acknowledged that both nucleation and growth of diamond on non-diamond surfaces without pre-treatment are very difficult and slow. Furthermore, the weak adhesion between the diamond thin films and substrates has been a major problem for widespread application of diamond thin films. Up to now, Si has been the most frequently used substrate for the study of diamond thin films and various methods, including bias and diamond powder scratching, have been applied to enhance diamond nucleation density. In the present study, nucleation and growth of diamond thin films on Ti3SiC2, a newly developed ceramic-metallic material, using Microwave Plasma Enhanced (MPE) and Hot-Filament (HF) CVD reactors were carried out. In addition, synchrotron-based Near Edge Extended X-Ray Absorption Fine Structure Spectroscopy (NEXAFS) was used to identify the electronic and chemical structures of various NCD films. The results from MPECVD showed that a much higher diamond nucleation density and a much higher film growth rate can be obtained on Ti3SiC2 compared with on Si. Consequently, nanocrystalline diamond (NCD) thin films were feasibly synthesized on Ti3SiC2 under the typical conditions for microcrystalline diamond film synthesis. Furthermore, the diamond films on Ti3SiC2 exhibited better adhesion than on Si. The early stage growth of diamond thin films on Ti3SiC2 by HFCVD indicated that a nanowhisker-like diamond-graphite composite layer, different from diamond nucleation on Si, initially formed on the surface of Ti3SiC2, which resulted in high diamond nucleation density. These results indicate that Ti3SiC2 has great potentials to be used both as substrates and interlayers on metals for diamond thin film deposition and application. This research may greatly expand the tribological application of both Ti3SiC2 and diamond thin films. The re.