The electronic and structural properties of amorphous and crystalline silicon hollow nanowires (HNWs) have been investigated by X-ray photoemission (XPS), Raman, and photoluminescence spectroscopies. The HNWs have an internal diameter of about 80 nm and sidewalls with a thickness of 8–15 nm. Crystalline HNWs are obtained by thermal annealing of the amorphous ones. XPS shows that although oxidation is a very important process in these suspended nanostructures, a clear Si 2p signal is detected in the crystalline HNWS, thus indicating that the sidewall surface maintains mainly a pure silicon nature. Raman shows that the thermal annealing gives rise to a very good crystal quality and a weak visible luminescence signal is detected in the crystalline HNWs.