A microstructural study of a TiN/Ti/4H-SiC stack is reported. The evolution of the stack with annealing has been studied by X ray-diffraction, X ray-reflectivity, Auger Electron Spectroscopy and Transmission Electron Microscopy for as-deposited, 300 degreesC, 500 degreesC and 800 degreesC annealed samples. Up to 500 degreesC, the crystalline structure of the Ti and TiN layers are unchanged and well-textured. An interfacial layer between Ti and SiC is evidenced by X-ray reflectivity and TEM. AES analysis reveals Ti-C bonds at the interface for all the annealing temperatures investigated. Oxygen diffusion at the interface after a 500 degreesC anneal is also shown. Annealing of the stack at 800 degreesC induces the formation of new crystalline phases consisting of Ti5Si3, C0.7N0.3Ti and titanium oxide as revealed by the XRD pattern.