The increasingly demand on secondary batteries with higher specific energy densities requires the replace- ment of the actual electrode materials. With a very high theoretical capacity (4200 mAh g−1 ) at low voltage, silicon is presented as a very interesting potential candidate as negative electrode for lithium-ion micro- batteries. For the first time, the electrochemical lithium alloying/de-alloying process is proven to occur, respectively, at 0.15 V/0.45 V vs. Li+ /Li with Si nanowires (SiNWs, 200-300 nm in diameter) synthesized by chemical vapour deposition. This new three-dimensional architecture material is well suited to accom- modate the expected large volume expansion due to the reversible formation of Li-Si alloys. At present, stable capacity over ten to twenty cycles is demonstrated. The storage capacity is shown to increase with the growth temperature by a factor 3 as the temperature varies from 525 to 575 ◦ C. These results, showing an attractive working potential and large storage capacities, open up a new promising field of research.