ABSTRACTPolytitanocarbosilane precursor for SiC/TiC ceramics was characterized by various spectroscopic techniques (29Si and 13C CP MAS NMR, Ti K-edge XANES and EXAFS) in order to follow how titanium ions are incorporated into the polycarbosilane-based polymer. This polymer has been fired in argon atmosphere, and the evolution of the local environments of Si and Ti atoms, during the pyrolysis process, have been followed using 29Si MAS-NMR and Ti K-edge X-ray absorption: this study reveals the formation of Si-O bonds above 500°C, while Ti-C bonds clearly appear around 800°C. Above 1000°C, Si-O bonds are consumed by reaction with excess carbon and the system finally crystallizes into SiC/TiC mixture above 1200°C.