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Amorphous SiO2 coating layers with thicknesses of ca. 2, 7, 10, and 15 nm are introduced into bulk@nanowire core@shell Si particles via direct thermal oxidation at 650-850 °C. Of the coated samples, Si with a coating thickness of ca. 7 nm has the best electrochemical performance. This sample shows an initial discharge capacity of 2279 mA h g(-1) with a Coulombic efficiency of 92% and displays 83% capacity retention after 50 cycles at 0.2C rate., (Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)