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To improve the interface bonding characteristics between copper and ceramic in Cu-(Ti3SiC2)p composites preparation, electroless copper plating on Ti3SiC2 powder surface and its electrochemical characteristics was investigated in this paper, using environmental friendly ascorbic acid as reducing agent and D-glucose sodium as complexing agent. The modified effects of lauryl sodium sulfate (SDS) combined Polysorbate 80 (Tween-80) surfactants on electroless copper plating was analyzed as well. Electrochemical mechanism and parameters optimization of this system was predetermined using linear sweep voltammetry and open circuit potential-time method. The results showed that the polarization current density could be improved by raising reaction temperature and the concentration of Cu (II) and ascorbic acid, which may certainly contribute to accelerate the process of electroless plating. New nuclei were developed from the Ag catalytic activated center implanted on the surface of the copper-coating (Ti3SiC2)p particle, and microspheres with more Ag catalytic active centers promote the formation of copper coatings. Modifying effect of combined modifiers with SDS ( 6-22 g/L) and Tween-80 (8-12 ml/L) were superior to single one. The total mole ratio of Cu to Ti3SiC2 of the best coating sample was 1:0.54, modified by SM4 (SDS and Tween-80 complex) modifier. Electrostatic effect together with steric hindrance effect play a crucial synergistic role for nuclei and growth controlling of copper on (Ti3SiC2)p surface.