The mechanical properties of titanium nitride (TiN) and related multicomponent films have been studied for decades. However, the virtues of TiN(100) coatings themselves and of their binding ability to Si(100) substrate are to be studied to ensure the application of transition layer for upper sediment, while the synergism between various growth parameters needs a further understanding. Herein, we present the mechanical properties of TiN(100), (111) planes and binding nature of Si(100)/TiN(100) interface by first principle. Then, TiN(100) films were epitaxially grown by pulse laser deposition (PLD) method on Si wafers under different conditions, and the structures, valence states, and properties were tested. We have obtained a high‐quality deposit with the hardness of ~31 GPa, which can firmly adhere on the substrate with high structural integrity, thus can be employed for further deposition of other oxide films. In general, higher substrate temperature and laser energy will improve the quality of the film. We anticipate that this study can give some hints on the properties of different crystal faces and the relationship of preparation variables during growing process.