A simple polymer pyrolysis method for the synthesis of hierarchically nanostructured NiFe2O4/C composites is reported in this study. The characteristics of the material are examined by thermogravimetry, X-ray diffraction and scanning electron microscopy. The electrochemical performances of the nanomaterial composites are investigated in detail. The results show that the obtained composite retains a high specific capacity of 780 mAh g−1 even after 40 cycles at a current density of 1/8C, and the coulombic efficiency approaches 99%. The reversible specific capacity can still be as high as 200 mAh g−1, at high rate of 4C. The nanostructured NiFe2O4/C composite is a potential competitive anode for lithium-ion batteries.