Hollow copper nanoparticle (Cu-NP) spheres with different wall thicknesses were prepared with organic and inorganic colloids as core combining self-assembly and electroless Cu deposition techniques. The hollow Cu-NP spheres made from polymeric colloids possessed a thicker wall but were easy to break in the removal of the core by THF, while those from SiO2 colloids had thinner wall and remained intact in the removal of the core by HF.