Thick-film electrodes of Si particles coated with Ni, Ni–Sn, and Ni–P were fabricated by electroless deposition followed by gas deposition to form the anode of a Li-ion battery. The electrode of Ni-coated Si showed remarkably improved cycling performance with a discharge capacity of 580mAhg−1 at the 1000th cycle, which is possibly caused by its higher elastic modulus than that of the uncoated Si electrode. The electrode of Si coated with Ni–P, which consisted of Ni3P, with the lower coating amount exhibited a higher initial capacity and excellent cycling performance with a capacity of 790mAhg−1 at the 1000th cycle, whereas poor performance was obtained for the electrode of Si coated with Ni–Sn. The excellent performance in the case of Ni–P coating is attributed to the smaller amount of coating, the high elastic modulus, and the lower reactivity of Ni3P with Li ions in comparison with Ni3Sn in Ni–Sn.