A nanostructured Ni-ferrite material, NiFe2O4, was successfully synthesized via facile co-precipitation in hot water, followed by an annealing process. The developed Ni-ferrite was face-centered cubic, highly crystalline, and nano-sized. The Ni-ferrite anode revealed superior electrochemical properties for Li-ion batteries, such as high reversible capacity and long cyclability, without significant capacity fading. Specifically, this anode exhibited reversible capacities of 926 and 1586 mAh g−1 at the 1st and 150th cycles at 0.1 A g−1, respectively. The superior electrochemical performance was attributed to the size and unique properties of the Ni-ferrite spinel. Nano-sized materials were beneficial for creating a large contact area between the electrode and electrolyte, increasing diffusion rates of lithium ions, resulting in enhanced pseudo-behavior. The properties of spinel structure and the presence of Fe and Ni metals during charge/discharge in Ni-ferrite prevented the destruction of the anode and catalyzed the decomposition of the Li2O phase, leading to extraordinary highly-reversible Li storage.