We describe a simple route for synthesizing electrically conductive Ag-coated Si anode materials with a high surface coverage via a simple chemical reduction process. A one-pot reduction process in the presence of alkylamine leads to a formation of Ag-coated Si particles at low temperature. The Ag-coated Si particles are highly dispersive and stable in aqueous and alcoholic solvents, and significantly enhance the poor electrical conductivity of Si particles. The electrically conductive Ag-coated Si electrodes exhibited excellent electrochemical performances, including a high reversible capacity (1550mAhg−1 at 0.1C rate), a stable cycling performance (a specific capacity of 1320mAhg−1 at 0.2C rate after 100 cycles), and excellent rate capability (a charge capacity of 640mAhg−1 at 5C rate). This simple route may open up an effective way to make other anode and cathode materials for practical lithium-ion battery applications.