We demonstrate a facile synthesis of micrometer-sized porous Si particles via copper-assisted chemical etching process. Subsequently, metal and/or metal silicide layers are introduced on the surface of porous Si particles using a simple chemical reduction process. Macroporous Si and metal/metal silicide-coated Si electrodes exhibit a high initial Coulombic efficiency of similar to 90%. Reversible capacity of carbon-coated porous Si gradually decays after 80 cycles, while metal/metal silicide-coated porous Si electrodes show significantly improved cycling performance even after 100 cycles with a reversible capacity of >1500 mAh g(-1). We confirm that a stable solid-electrolyte interface layer is formed on metal/metal silicide-coated porous Si electrodes during cycling, leading to a highly stable cycling performance.