Mo powders with average particle size of 3 μm were attempted to coat with copper by electroless plating technique. The effect of the solution composition and plating conditions on the electroless copper plating was studied. The uncoated and coated powders were subjected to the microstructural studies by SEM and the phases were analyzed by XRD. The results indicate that the Mo powders are coated with copper,at the same time,Mo-Cu composite powders with Cu content ranging from 15% to 85%(mass fraction) can be obtained. The optimal values of pH,HCHO concentration and temperature are in the ranges of 12-13,22-26 ml/L and 60-65 ℃,respectively. The diffusion-shrinkage autocatalytic model is suggested for the growth mechanism of electroless coating over the surface.