TiB2 thin film was deposited by laser-arc deposition method on the surface of single crystalline silicon. The morphology, composition, structure and microtribological properties of the film were studied by using XPS, XRD and atomic force/friction force microscope (AFM/FFM). The results show that TiB2 (100) preferred growth on the Si(100) substrate, TiB2(001) preferred growth on the Si(111) substrate. The TiB2 thin film was composed of TiB2 and a small amount of TiO2. The friction coefficient of TiB2 film on substrates Si (100) and Si(111) in microtribological process were 0.087 and 0.073, respectively. TiB2 thin film displayed distinct ability of anti-scratch and wear-resistance.