The multi-walled carbon nanotubes (MWCNTs, mean diameter: 100-200nm) with nickel-phosphorous (Ni-P) coatings were obtained by an electroless deposition process. To prepare the MWCNTs covered with continual Ni-P layers, a pre-treatment procedure comprised of acid-cleaning, sensitization and activation has been developed. The resulting MWCNTs have a uniform distribution of the Ni-P layers coated on the MWCNTs with the fibrous appearance maintained. X-ray diffraction (XRD) and transmission electron microscopy (TEM) observations revealed that the as-coated MWCNTs were comprised of the amorphous Ni-P layers and inner carbon nanotubes covered with the Ni-P layers. These amorphous Ni-P-coated MWCNTs were used as precursors for preparing MWCNTs with nanocrystalline Ni-P(crystalline Ni and Ni3P intermetallic compound) layers by the heattreatment above 400℃, which were determined by differential scanning calorimeter (DSC) and XRD studies. The results of this work provide an effective electrochemical method for preparing powdery MWCNTs with Ni-P layer as new composite materials from the aqueous solution.