Deposition of a heteroepitaxial TiHfN film with a growth rate of about 1 μm/h was successfully achieved on a Si (001) substrate at a temperature above 700 °C by direct current magnetron reactive sputtering of a Ti_0.6Hf_0.4 (in atomic fraction) target with an Ar/N₂ gas mixture. Annealing of the as-deposited TiHfN/Si sample at a temperature above 1000 °C using microwave plasma with H₂/N₂ gas was performed to further improve the TiHfN film’s quality. X-ray diffraction results show that the heteroepitaxial TiHfN film on Si exhibits a cube-on-cube relationship as {001}_TiHfN//{001}_Si and _TiHfN//_Si. X-ray rocking curve measurements show that the full width at half maximum of (200)_TiHfN is 1.36° for the as-deposited TiHfN film, while it is significantly reduced to 0.53° after microwave plasma annealing. The surface morphologies of the as-deposited and annealed TiHfN films are smooth, with a surface roughness of around ~2 nm. Cross-sectional scanning/transmission electron microscopy (S/TEM) shows a reduction in defects in the annealed film, and X-ray photoelectron spectroscopy shows that the film composition remains unchanged. Additionally, S/TEM examinations with atomic resolution illustrate domain matching epitaxy (DME) between TiHfN and Si at the interface. The TiHfN films have good electrical conducting properties with resistivities of 40–45 μΩ·cm.