A superhydrophobic surface of titanium was fabricated by anodization in sodium chloride solution followed by immersion in perfluorodecyltriethoxysilane. The surface characteristics of the anodic film (morphology, composition, microstructure, and adhesion) were investigated by scanning electron microscopy, transmission electron microscopy, X‐ray photoelectron spectroscopy, and scratch testing. The anodic film was comprised of TiO2 and TiCl3 with a thickness of 50 nm. The anodized titanium surface exhibited a hierarchical structure, which consisted of a microscale horn structure with a nanoscale strip‐overlay. This structure provided superhydrophobicity (water contact angle: 151.9° and sliding angle: 3°) following the immersion process. Furthermore, coverage of the hierarchical structure on the anodized titanium surface was improved by performing surface mechanical attrition treatment (SMAT) to grain‐refine titanium surface which was then anodized and it enhanced a slightly increased water contact angle. The thickness (200 nm) of the anodic film on the SMAT‐pretreated titanium surface was much higher than that on the titanium surface (50 nm). This resulted from a large number of grain boundaries on the surface serving as a fast diffusion path during anodization. However, the adhesion of the SMAT‐and‐anodized film was worse than that formed by anodization only. This is due to a large number of pores within the SMAT‐and‐anodized film.