The atomic and electronic structures of small-sized Ni n (n = 2−10) clusters supported on the anatase TiO 2 (101) surface [denoted as A(101)] are systematically investigated by an extensive evolutionary structural search and density functional theory calculations. The predicted low-energy structures show that 3D geometries are more favored for most supported Ni n clusters. Thermodynamic stability analysis indicates that the cluster−substrate interaction plays a critical role in stabilizing the Ni n /A(101) system. Ni 4 /A(101), Ni 6 /A(101), and Ni 8 /A(101) are more stable compared to their neighbors and may be easily formed experimentally. Electrons transfer from the supported Ni n clusters to the TiO 2 substrate and mostly accumulate at the Ti 5c sites just below the Ni n cluster. These extra electrons may easily transfer to other surface sites, enhancing the reactivity of the TiO 2 surface, and can also transfer back to the Ni n cluster, providing additional active sites besides the metallic Ni atoms. Moreover, the introduction of Ni n clusters can enhance the visible light response of the system. The results of this work indicate that Ni n /TiO 2 systems are promising high-performance photocatalysts or electrocatalysts for efficient N 2 reduction reactions and NH 3 synthesis.