The synthesis of trimethylsilyl-substituted poly(titaniumcarbodiimide) as a novel precursor for titanium carbonitride based ceramic materials is described. The precursor and the subsequent processing steps (cross-linking and pyrolysis) are characterized by IR and Raman spectroscopy, thermal gravimetric analysis and simultaneous mass spectroscopy, electron microscopy and powder X-ray diffraction measurements. The novel polymer is formed by the reaction of TiCl 4 or Ti(NEt 2 ) 4 with bis(trimethylsilyl)carbodiimide. Subsequent pyrolysis at 1000°C in argon results in the formation of a ceramic composite material consisting of nanocrystalline TiCN and amorphous SiCN as constituting phases. Using Ti(NEt 2 ) 4 as a starting reagent instead of TiCl 4 , chlorine contamination of the ceramic material can be avoided. The different molecular vibration modes of the metal-nitrogen, metal-carbon and nitrogencarbon bonds in poly(titaniumcarbodiimides) with trimethylsilyl substituents were calculated using quantum mechanical methods, providing a comprehensive understanding of the measured spectra.