In this study, Cu-coated Al2O3 composite powders were synthesized by using electroless plating method. The inuence of the plating bath composition and ceramic powder concentration on the Cu plating was characterized by scanning electron microscopy, energy dispersive spectroscopy, and X-ray diraction techniques. The results showed that the electroless bath composition plays an important role for the structure of nano core-shell Al2O3/Cu composite powders. The content of copper in the composite powders could be eectively controlled by adjusting the content of copper sulfate and formaldehyde in the plating solution. Furthermore, the pretreatment of the Al2O3 powders is also a key factor to form a uniform shell copper layer coating on Al2O3 particles.