Silicon, with its elaborate microstructure, plays important roles in energy materials. In operando engineering of microstructure during extraction is an ideal protocol to develop advanced Si‐based materials. A template‐free electrochemical preparation of silicon nanotubes (Si‐NT) is herein achieved by co‐electrolysis of SiO2 and AgCl in molten NaCl–CaCl2 at 850 °C. The in situ electrodeposited Ag facilitates the generation of a liquid Ag–Si intermediate, triggering a liquid–solid mechanism to direct the growth of Si‐NT. An automatic separation of Ag from Si then occurs in the following cooling process, resulting in Ag deposits on the Ni current collector and recycling of Ag. Such a facile and smart preparation of Si‐NT from affordable silica guarantees an enhanced current efficiency of 74%, a decreased energy consumption of 12.1 kW h kgSi−1, and enhanced lithium‐storage capability of the electrolytic Si‐NT. An in situ coating of Ag over the Si‐NT can also be fulfilled by simply introducing soluble AgCl in the melts. The present study provides a template‐free preparation and an in situ surface modification of Si‐NT.

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