Single-crystalline silicon nanowires (SiNWs) were fabricated by using an electroless metal-assisted etching of bulk silicon wafers with silver nanoparticles obtained by wet electroless deposition. The etching of SiNWs is based on sequential treatment in aqueous solutions of silver nitrate followed by hydrofluoric acid and hydrogen peroxide. SEM observation shows that well-aligned nanowire arrays perpendicular to the surface of the Si substrate were produced. Free-standing SiNWs were then obtained using ultrasono-method in toluene. Alkyl-derivatized SiNWs were prepared to prevent the aggregation of SiNWs and obtained from the reaction of SiNWs and dodecene via hydrosilylation. Optical characterizations of SiNWs were achieved by FT-IR spectroscopy and indicated that the surface of SiNWs is terminated with hydrogen for fresh SiNWs and with dodecyl group for dodecyl-derivatized SiNWs, respectively. The main structures of dodecyl-derivatized SiNWs are wires and rods and their thicknesses of rods and wire are typically 150-250 and 10-20 nm, respectively. The morphology and chemical state of dodecyl-derivatized SiNWs are characterized by scanning electron microscopy, transmission electron microscopy, and X-ray photoelectron spectroscopy.