An advantageous procedure has been developed, allowing metallization of multi-walled carbon nanotubes (MWCNTs, mean diameter: 50-80nm) with Cu layer by an electroless deposition process. Such a procedure for achieving electroless Cu deposition on MWCNTs involves acid pre-clean, sensitization and activation. Results show that metallizated MWCNTs keep the fiber-like appearances with uniform distribution. This resulting nanotube-derived material is comprised of a nanocrocrystalline Cu layer and inner nanotube covered with Cu layer. The results of this work have demonstrated the effectiveness of electroless deposition on the metallization of MWCNTs.