Thick film electrodes consisting of Ru and Ru-coated Si particles were fabricated by a gas-deposition method and their electrochemical properties of anodes for Li rechargeable battery were evaluated. The discharge capacity of the Ru electrode at 1000th cycle is approximately 400mAhg−1. The result showed that the electrode reaction is based on the redox reaction of RuO2 which was formed on the Ru surface during the charge–discharge processes. By coating Si particles with Ru using an electroless deposition technique, we obtained an electrode with remarkable discharge capacity of 570mAhg−1 at 1000th cycle. The reason for the improvement in the electrode performance appears to result from the fact that the Ru electrode exhibits excellent cycleability itself and the Ru coated on Si reduces the stress generated by the immense volumetric changes occurring in the Si particles.