The effects of electroless coatings on the microstructure and composition of the interface between multi-walled carbon nanotubes (MWCNTs) and a Cu matrix and the mechanical properties and wear behavior of the resulting copper matrix composites were investigated. Ni and Cu coatings were electrolessly plated on MWCNTs and mixed subsequently with copper powder. Then copper matrix composites were prepared by sintering, hot extrusion and cold drawing processes. The results showed that MWCNTs were straight, long, uniformly dispersed and aligned in the composites. The Ni coating is more continuous, dense and complete than a Cu coating. The tensile strength, compressive strength, microhardness and tribological properties of Ni@MWCNTs/Cu composite along the drawing direction were enhanced most. The ultimate tensile strength and compressive strength were 381 MPa and 463 MPa, respectively. The friction coefficient and wear rate were reduced by 59% and 77%, respectively, compared with pure Cu samples. This study provides a new insight into the regulation of tribological properties of composites by their interface.