Nano-structured and micro/nano-hierarchical structured TiO2 coatings were produced on polished titanium by the micro-arc oxidation (MAO) technique. This study was conducted to screen a suitable structured TiO2 coating for osteoblast adhesion and differentiation in dental implants. The formulation was characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), and wettability testing. Adhesion, proliferation, and osteogenic differentiation of MG63 cells were analysed by SEM, Cell Counting Kit-8 (CCK-8), and quantitative real-time PCR. The micro/nano-hierarchical structured TiO2 coating with both slots and pores showed the best morphology and wettability. XRD analysis revealed that rutile predominated along with a minor amount of anatase in both TiO2 coatings. Adhesion and extension of MG63 cells on the micro/nano-hierarchical structured TiO2 coating were the most favourable. MG63 cells showed higher growth rates on the micro/nano-hierarchical structured TiO2 coating at 1 and 3 days. Osteogenic-related gene expression was markedly increased in the micro/nano-hierarchical structured TiO2 coating group compared to in the polished titanium group at 7, 14, and 21 days. These results revealed the micro/nano-hierarchical structured TiO2 coating as a promising surface modification and suitable biomaterial for use with dental implants.