The surface engineering strategy has exhibited unique advantages in photocatalysis, electrocatalysis, sensing, etc. Here in this work, NiO nano octahedron aggregates with exposure of active {111} facets are synthesized through a facile and scalable way. When evaluated as anode materials for Li ion batteries (LIBs), the NiO nano octahedron aggregates exhibit excellent rate performance and long-life cycling performance with high reversible capability. A reversible capability of as high as 793mAhg−1 is retained after 200 cycles at 0.2C. Moreover, the excellent rate performance is achieved. The exceeding lithium storage performance is attributed to the synergy effect of nano size and exposed (111) surface of the NiO octahedra improving kinetics of charge transportation and Li ion diffusion. The NiO octahedron aggregates can be used as prospective host materials for investigation of surface effect on catalysis, sensing, switching, supercapacitors and electrodes for sodium batteries, fuel cells, etc.