Copper coated nano-SiO2 composite particles were prepared by mechanical milling technology. The effects of milling time on morphology, granularity, component and microstructure of the composite particles were characterized by scanning electronic microscope, laser particle size analyzer, energy depressives spectrometer and transmission electron microscope, respectively. Results showed that dendrite composite particles change to the flaky, and then to spherical ones with the milling time increasing. The particle size decreases firstly and then increases with the milling time increasing. The n-SiO2 particles disperse more homogeneously in the composite particles with the milling time increasing.