Iron-based oxides are widely used in lithium-ion batteries due to their abundant reserves, low cost and high specific capacity. Nevertheless, low intrinsic conductivity and large volume changes during Li+ embedding seriously hinder its application. In this paper, hexahedral NiFe2O4/Ni particles with regular morphology were prepared by solvothermal method and high temperature calcination. The phase content of the product was controlled by adjusting the ratio of the feed amount during synthesis and used in lithium-ion batteries. Composites with optimal ratios (2Fe-Ni-2*3p) shows excellent electrochemical performance after 100 cycles (916.7 mAh g−1 at 0.1 A g−1). What is noteworthy is that the 2Fe-Ni-2*3p composite with this ratio still possesses a respectable capacity of 611.2 mAh g−1 at high current 1 A g−1. The results show that a certain amount of Ni has an important effect on the conductivity of materials. In addition, the lithium-ion diffusion coefficient of 2Fe-Ni-2*3p composites was higher than that of other composites by the test of galvanostatic intermittent titration technique (GITT). Hence, the design strategy of this material could pave the way for LIBs materials.