Abstract: The growth behavior containing deposit morphology, growth rate, activation energy, and growth mechanism of copper on silicon substrate, especially at the initial stage, in the electroless plating process was studied. Copper was deposited on the surface of the silicon substrate in an electloless plating bath containing formalin (CH₂O 37vol%) as a reducing agent at a pH value of 12.5 and a temperature of 50-75℃. The copper deposit was characterized using a field emission scanning electron microscope and transmission electron microscope. The results showed that after the activation process, nanoscale Pd particles were distributed evenly on the surface of the silicon; in the deposition process, copper first nucleated at locations not only near the Pd particles but also between the Pd particles; the growth rate of electroless Cu ranged from 0.517 nm/s at 50℃ to 1.929 nm/s at 75℃. The activation energy of electroless Cu on Si was 52.97 kJ/mol.