Growth of epitaxial TiN film on a semi-insulating single crystal (0001) SiC substrate has been achieved by DC magnetron reactive sputtering deposition. The effects of growth temperature and N2 flow ratio in Ar on film quality and growth rate were investigated. X-ray diffraction (XRD) characterization shows that all the deposited TiN films at 550 and 700 °C are heteroepitaxially grown on SiC with the epitaxial relationship between TiN and 4H-SiC in (111)TiN//(0001)SiC and [11¯0]TiN//[112¯0]4H-SiC. Increasing the N2 flow ratio from 4 to 8% results in improvement of the film quality and a decrease in the growth rate. The width of the X-ray rocking curve of TiN (111) reflection can reach a value as small as 249 arcsec and the resistivity of TiN film can be 21 μΩ·cm for deposition at 700 °C with 8% N2 flow ratio. Measurements by atomic force microscopy show that the surface roughness of the TiN film can be 1.1 nm. X-ray photoelectron spectroscopy reveals that TiN composition is nearly in stoichiometry for all the grown TiN films. Examinations by cross-sectional transmission electron microscopy show that TiN is directly grown on SiC and verify the epitaxial relationship from XRD.