Nanodiamond/Ni and Ni coatings were fabricated via brush plating. Nanocrystalline structure of the composite coating was investigated by SEM and XRD. The results showed that the composite coatings are nanocrystalline structure. The hardness of the nanodiamond/Ni composite coating is higher greatly than that of Ni coating. At same time, the reasons of formation nanocrystalline were discussed, which include the nucleation rate with the increase of a high over-potential, the reciprocating motion between brush and work piece, the heterogeneous nucleation of nanodiamond. The nanodiamonds as second phases make grain finer. The nanodiamonds of core-shell structure play the important role in wear resistance and antifriction. So the wear resistance of the composite coatings is significantly higher than nickel coating’s.