This review outlines the developments and recent progress in metal-assisted chemical etching of silicon, summarizing a variety of fundamental and innovative processes and etching methods that form a wide range of nanoscale silicon structures. The use of silicon as an anode for Li-ion batteries is also reviewed, where factors such as film thickness, doping, alloying, and their response to reversible lithiation processes are summarized and discussed with respect to battery cell performance. Recent advances in improving the performance of silicon-based anodes in Li-ion batteries are also discussed. The use of a variety of nanostructured silicon structures formed by many different methods as Li-ion battery anodes is outlined, focusing in particular on the influence of mass loading, core-shell structure, conductive additives, and other parameters. The influence of porosity, dopant type, and doping level on the electrochemical response and cell performance of the silicon anodes are detailed based on recent findings. Perspectives on the future of silicon and related materials, and their compositional and structural modifications for energy storage via several electrochemical mechanisms, are also provided.