Nickel and copper were coated on Si particles by a stepwise electroless deposition technique in which the coating orders of the metals were exchanged. Thick-film electrodes for Li-ion batteries were prepared by a gas-deposition method using the coated Si particles, and the anode performance of these electrodes was investigated. For (Cu, Ni)-coated Si particles obtained by primary Cu deposition and successive Ni deposition, Cu and Ni metal layers were individually deposited on the Si particles. In contrast, in case of (Ni, Cu)-coated Si particles prepared by primary Ni deposition, Cu layer stacked on Ni layer owing to a high catalytic activity of Ni, forming a thicker coated layer. The latter electrode exhibited notably improved performance with the discharge capacities over 1000mAhg−1 maintained until 400th cycle. The layer stack of Cu on Ni is probably effective for a release of a stress from the Si particles during charge–discharge reactions.