Si/Ni alloy and graphite composites were synthesized using arc-melting followed by high energy mechanical milling (HEMM). Alloy particles comprising of NiSi2, NiSi and Si phases were distributed finely and uniformly on the surface of graphite in the composites obtained after HEMM. The composite containing 60wt.% of Si/Ni alloy exhibited a stable capacity of ∼780mAh/g. Fourier transform infrared spectroscopy (FTIR) analysis confirmed that some bonds were formed between alloy and graphite after HEMM, which appeared to retain the electrical connection between alloy and graphite during cycling. X-ray diffraction (XRD) analysis indicated that NiSi2 and NiSi phases, which acted as an inactive alloy matrix remained invariant during charge and discharge. In addition to NiSi2 and NiSi phases, disordered graphite layers also played the role of media for the accommodation of large volume change of Si during cycling. The large reversible capacity and good cycleability showed that Si/Ni alloy and graphite composite could be an alternative to conventional graphite-based anode materials for lithium-ion secondary batteries.