High-areal-density Sn nanowires (NWs) with diameter of ≥25nm and length of several micrometers (>103 aspect ratio) were successfully prepared via template-free electrodeposition from organic solutions containing SiCl4 and an ionic liquid (IL). This study shows that the presence of both IL and SiCl4 in the electrolyte is necessary to obtain structurally well-defined NWs. Electron microscopy, energy-dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy demonstrate that the NWs consist of high-quality β-Sn crystallites and the morphology is homogenous over large deposition areas. It is also shown that various organic solvents such as propylene carbonate and acetonitrile as well as different types of ILs as supporting electrolytes in combination with SiCl4 can be used for the preparation of Sn NWs. This makes the electrochemical synthesis flexible in terms of solubility parameter and less costly than deposition from pure ILs. The Sn NWs were also tested for application in rechargeable Li-ion cells by galvanostatic cycling against Li metal. The electrodes were found capable of delivering stable specific capacities of around 680mA h gSn −1 at C/5 over several cycles.